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It is now recognized that analytical chemistry must also be a target for green principles, in particular chromatographic methods which typically use relatively large volumes of hazardous organic solvents. More generally, high performance liquid chromatography (HPLC) is employed routinely for quality control of complex mixtures in various industries. Acetonitrile and methanol are the most commonly used organic solvents in HPLC, but they generate an impact on the environment and can have a negative effect on the health of analysts. Ethanol offers an exciting alternative as a less toxic, biodegradable solvent for HPLC. In this work we demonstrate that replacement of acetonitrile with ethanol as the organic modifier for HPLC can be achieved without significantly compromising analytical performance. This general approach is demonstrated through the specific example analysis of a complex plant extract. A benchmark method employing acetonitrile for the analysis of Bidens pilosa extract was statistically optimized using the Green Chromatographic Fingerprinting Response (GCFR) which includes factors relating to separation performance and environmental parameters. Methods employing ethanol at 30 and 80°C were developed and compared with the reference method regarding their performance of separation (GCFR) as well as by a new metric, Comprehensive Metric to Compare Liquid Chromatography Methods (CM). The fingerprint with ethanol at 80°C was similar to or better than that with MeCN according to GCFR and CM. This demonstrates that temperature may be used to replace harmful solvents with greener ones in HPLC, including for solvents with significantly different physiochemical properties and without loss in separation performance. This work offers a general approach for the chromatographic analysis of complex samples without compromising green analytical chemistry principles.

AbstractSome cases of occurrence of matrix effects (mostly ion suppression) in protein‐precipitated plasma samples, and their influence on the validity of plasma concentrations and pharmacokinetic parameters, are discussed. The comparison of matrix effects using either electrospray (TurboIonspray, TISP) or atmospheric pressure chemical ionization (APCI) indicated that APCI is less prone to matrix effects. Nevertheless, TISP is usually the first choice of ionization technique since unknown thermally labile metabolites might be present in the plasma samples causing erroneous results. A high impact of ion suppression on the plasma concentrations after intravenous (i.v.) administration was found, depending on the drug formulation (vehicle). Since ion suppression caused significantly lower plasma concentrations (by a factor of up to 5.5) after i.v. dosing, the area under the curve (AUC) was underestimated and the plasma clearance was consequently erroneously high, with an impact on drug candidate selection. By simple stepwise dilution (e.g. 10‐fold and 50‐fold) of the supernatant of protein‐precipitated plasma samples, including all calibration and quality control samples, the matrix effects were recognized and eliminated. Copyright © 2003 John Wiley & Sons, Ltd.

Endocrinological research on wild animals inhabiting remote areas has been hampered by the need to store plasma samples at subzero temperatures. In an attempt to remedy this logistical issue, we here investigate the use of ethanol as an alternative to freezing for the preservation of steroid and indoleamine hormones in avian plasma. Known quantities of the steroids 5alpha-dihydrotestosterone (DHT), testosterone, 17beta-estradiol, corticosterone, and the indoleamine melatonin were added to a stripped pool of chicken plasma. Samples were either immediately frozen at -40 degrees C, or treated with pure ethanol. Ethanol-treated samples were either immediately frozen, or-to simulate storage conditions at various field locations-left sitting at room temperature for one to two months, or incubated at 36 degrees C for one month before all treatment groups were frozen at -40 degrees C. All samples were then analyzed by radioimmunoassay. For DHT and estradiol there were no differences among treatment groups suggesting that ethanol-treatment is as effective as immediate freezing in preserving plasma steroid concentrations. For testosterone, corticosterone and melatonin ethanol-treated samples differed significantly from immediately frozen samples suggesting that caution is needed when comparing absolute concentrations of hormones between samples preserved in different ways. However, differences among ethanol-treated samples in general were small, demonstrating the feasibility of this preservation method in the field at remote locations.

AbstractCoral reefs across the world have been seriously degraded and have a bleak future in response to predicted global warming and ocean acidification (OA). However, this is not the first time that biocalcifying organisms, including corals, have faced the threat of extinction. The end‐Triassic mass extinction (200 million years ago) was the most severe biotic crisis experienced by modern marine invertebrates, which selected against biocalcifiers; this was followed by the proliferation of another invertebrate group, sponges. The duration of this sponge‐dominated period far surpasses that of alternative stable‐ecosystem or phase‐shift states reported on modern day coral reefs and, as such, a shift to sponge‐dominated reefs warrants serious consideration as one future trajectory of coral reefs. We hypothesise that some coral reefs of today may become sponge reefs in the future, as sponges and corals respond differently to changing ocean chemistry and environmental conditions. To support this hypothesis, we discuss: (i) the presence of sponge reefs in the geological record; (ii) reported shifts from coral‐ to sponge‐dominated systems; and (iii) direct and indirect responses of the sponge holobiont and its constituent parts (host and symbionts) to changes in temperature andpH. Based on this evidence, we propose that sponges may be one group to benefit from projected climate change and ocean acidification scenarios, and that increased sponge abundance represents a possible future trajectory for some coral reefs, which would have important implications for overall reef functioning.

Abstract The expansion of Sargassum muticum in the Danish estuary Limfjorden between 1984 and 1997 was followed by a decrease in abundance of native perennial macroalgae such as Halidrys siliquosa. Although commonly associated with the expansion of exotic species, it is unknown whether such structural changes affect ecosystem properties such as the production and turnover of organic matter and associated nutrients. We hypothesized that S. muticum possesses ‘ephemeral’ traits relative to the species it has replaced, potentially leading to faster and more variable turnover of organic matter. The biomass dynamics of S. muticum and H. siliquosa was therefore compared in order to assess the potential effects of the expansion of Sargassum. The biomass of Sargassum was highly variable among seasons while that of Halidrys remained almost constant over the year. Sargassum grew faster than Halidrys and other perennial algae and the annual productivity was therefore high (P/B = 12 year−1) and exceeded that of Halidrys (P/B = 5 year−1) and most probably also that of other perennial algae in the system. The major grazer on macroalgae in Limfjorden, the sea urchin Psammechinus miliaris, preferred Sargassum to Halidrys, but estimated losses due to grazing were negligible for both species and most of the production may therefore enter the detritus pool. Detritus from Sargassum decomposed faster and more completely than detritus from Halidrys and other slow-growing perennial macrophytes. High productivity and fast decomposition suggest that the increasing dominance of S. muticum have increased turnover of organic matter and associated nutrients in Limfjorden and we suggest that the ecological effects of the invasion to some extent resemble those imposed by increasing dominance of ephemeral algae following eutrophication.

This study highlights how Chinese economic development detrimentally impacted water quality in recent decades and how this has been improved by enormous investment in environmental remediation funded by the Chinese government. To our knowledge, this study is the first to describe the variability of surface water quality in inland waters in China, the affecting drivers behind the changes, and how the government-financed conservation actions have impacted water quality. Water quality was found to be poorest in the North and the Northeast China Plain where there is greater coverage of developed land (cities + cropland), a higher gross domestic product (GDP), and higher population density. There are significant positive relationships between the concentration of the annual mean chemical oxygen demand (COD) and the percentage of developed land use (cities + cropland), GDP, and population density in the individual watersheds (p < 0.001). During the past decade, following Chinese government-financed investments in environmental restoration and reforestation, the water quality of Chinese inland waters has improved markedly, which is particularly evident from the significant and exponentially decreasing GDP-normalized COD and ammonium (NH4+-N) concentrations. It is evident that the increasing GDP in China over the past decade did not occur at the continued expense of its inland water ecosystems. This offers hope for the future, also for other industrializing countries, that with appropriate environmental investments a high GDP can be reached and maintained, while simultaneously preserving inland aquatic ecosystems, particularly through management of sewage discharge.

Abstract Amorphous and microcrystalline silicon single layers and p–i–n solar cells were produced dynamically using an inline deposition system called “line source”. A highly uniform deposition of thin-film silicon layers with layer-thickness variations of less than ±5% was achieved. Amorphous and microcrystalline silicon single junction solar cells were dynamically fabricated with initial efficiencies of 8.3% and 6.3%, respectively. The dynamic deposition rate of these solar cells is 6.75 nm m/min in case of a-Si:H and 3.3 nm m/min for μc-Si:H. In this work it will be shown that an enhancement of the deposition rate up to 15.6 nm m/min during the i-layer deposition of a-Si:H solar cells has only a weak negative influence on the initial efficiencies of the cells. Further on, the effect of substrate velocity on solar cell characteristics of a-Si:H solar cells is investigated. Finally, a productivity estimation of the line source concept is presented.

Abstract Solutions containing hydrofluoric acid (HF), hydrochloric acid (HCl), and hydrogen peroxide (H2O2) were investigated as novel acidic, NOx-free etching mixtures for texturing of monocrystalline silicon wafers. High etch rates of up to 13.3 nm s−1 were observed at room temperature, which are comparable to the etch rates of KOH-IPA solutions. The silicon surface was investigated by scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM), indicating pyramidal textures for diamond wire and SiC-slurry sawn as well as saw-damage etched (polished) wafers. Non-stirred baths generate random pyramidal structures while constantly stirred solutions generate novel random inverted pyramidal surface structures. The light trapping efficiency of wafers etched by the HF-HCl-H2O2 solutions was compared by UV/vis-reflectivity measurements to KOH/i-propanol specimens indicating lower reflectivities for the HF-HCl-H2O2-treated samples. Using the ‘wafer ray tracer’ (pvlighthouse.com) the light absorption properties of monomodal and random inverted pyramid structures were simulated and compared to well-known random and monomodal textures for PERC solar cells, clearly indicating the best performance for random inverted pyramids. Besides, simulation of a PERC solar cell on a roof top at our university was performed, indicating improved performance, especially for random inverted pyramid textures.