Impact of paleoclimate on present and future evolution of the Greenland Ice Sheet.

Using transient climate forcing based on simulations from the Alfred Wegener Institute Earth System Model (AWI-ESM), we simulate the evolution of the Greenland Ice Sheet (GrIS) from the last interglacial (125 ka, kiloyear before present) to 2100 AD with the Parallel Ice Sheet Model (PISM). The impact of paleoclimate, especially Holocene climate, on the present and future evolution of the GrIS is explored. Our simulations of the past show close agreement with reconstructions with respect to the recent timing of the peaks in ice volume and the climate of Greenland. The maximum and minimum ice volume at around 18-17 ka and 6-5 ka lag the respective extremes in climate by several thousand years, implying that the ice volume response of the GrIS strongly lags climatic changes. Given that Greenland's climate was getting colder from the Holocene Thermal Maximum (i.e., 8 ka) to the Pre-Industrial era, our simulation implies that the GrIS experienced growth from the mid-Holocene to the industrial era. Due to this background trend, the GrIS still gains mass until the second half of the 20th century, even though anthropogenic warming begins around 1850 AD. This is also in agreement with observational evidence showing mass loss of the GrIS does not begin earlier than the late 20th century. Our results highlight that the present evolution of the GrIS is not only controlled by the recent climate changes, but is also affected by paleoclimate, especially the relatively warm Holocene climate. We propose that the GrIS was not in equilibrium throughout the entire Holocene and that the slow response to Holocene climate needs to be represented in ice sheet simulations in order to predict ice mass loss, and therefore sea level rise, accurately.

Structural studies of DNA end detection and resection in homologous recombination.

DNA double-strand breaks are repaired by two major pathways, homologous recombination or nonhomologous end joining. The commitment to one or the other pathway proceeds via different steps of resection of the DNA ends, which is controlled and executed by a set of DNA double-strand break sensors, endo- and exonucleases, helicases, and DNA damage response factors. The molecular choreography of the underlying protein machinery is beginning to emerge. In this review, we discuss the early steps of genetic recombination and double-strand break sensing with an emphasis on structural and molecular studies.

Human hair in the identification of cocaine abuse with cantilever-enhanced photoacoustic spectroscopy and principal component analysis.

In this study, a novel approach combining different techniques, including Fourier transform infrared (FT-IR) spectroscopy, photoacoustic spectroscopy (PAS) with an interferometric cantilever microphone, and principal component analysis (PCA) along with a proper data preprocessing procedure, have been used in the investigation of hair samples for cocaine abuse. Hair fibers from cocaine-overdose patients have been measured using a simple procedure involving cantilever-enhanced photoacoustic Fourier transform infrared spectroscopy. In addition, a reference group of hair samples from subjects with no cocaine abuse has been measured. We present a first approach to discriminate the cocaine users from the reference group with the photoacoustic method and PCA. With proper data preprocessing methods, the two groups were successfully separated according to their spectra. The results were confirmed with two different classification methods independent of the principal component data analysis.

FT-IR-cPAS--new photoacoustic measurement technique for analysis of hot gases: a case study on VOCs.

This article describes a new photoacoustic FT-IR system capable of operating at elevated temperatures. The key hardware component is an optical-readout cantilever microphone that can work up to 200 °C. All parts in contact with the sample gas were put into a heated oven, incl. the photoacoustic cell. The sensitivity of the built photoacoustic system was tested by measuring 18 different VOCs. At 100 ppm gas concentration, the univariate signal to noise ratios (1σ, measurement time 25.5 min, at highest peak, optical resolution 8 cm(-1)) of the spectra varied from minimally 19 for o-xylene up to 329 for butyl acetate. The sensitivity can be improved by multivariate analyses over broad wavelength ranges, which effectively co-adds the univariate sensitivities achievable at individual wavelengths. The multivariate limit of detection (3σ, 8.5 min, full useful wavelength range), i.e., the best possible inverse analytical sensitivity achievable at optimum calibration, was calculated using the SBC method and varied from 2.60 ppm for dichloromethane to 0.33 ppm for butyl acetate. Depending on the shape of the spectra, which often only contain a few sharp peaks, the multivariate analysis improved the analytical sensitivity by 2.2 to 9.2 times compared to the univariate case. Selectivity and multi component ability were tested by a SBC calibration including 5 VOCs and water. The average cross selectivities turned out to be less than 2% and the resulting inverse analytical sensitivities of the 5 interfering VOCs was increased by maximum factor of 2.2 compared to the single component sensitivities. Water subtraction using SBC gave the true analyte concentration with a variation coefficient of 3%, although the sample spectra (methyl ethyl ketone, 200 ppm) contained water from 1,400 to 100k ppm and for subtraction only one water spectra (10k ppm) was used. The developed device shows significant improvement to the current state-of-the-art measurement methods used in industrial VOC measurements.

Fourier transform infrared photoacoustic multicomponent gas spectroscopy with optical cantilever detection.

The sensitivity of photoacoustic spectroscopy was improved with the invention of optical cantilever detection (PAS-OCD). However, the ability of present PAS-OCD devices to carry out multicomponent detection is poor. To overcome this, a Fourier transform infrared photoacoustic spectrometer with optical cantilever detection (FT-IR-PAS-OCD) prototype was assembled. In this article, the first evaluation and performance tests of the prototype are described. Selectivity, sensitivity, and the linearity of the signal response are evaluated. The linear response was studied for methane and carbon dioxide and confirmed in the whole analyzed concentration range from 500 to 3500 ppm and from 2500 to 17500 ppm, respectively. The calculated signal-to-noise ratio (SNR) and limit of detection were 2027 and 0.5 ppm for methane and 1362 and 4 ppm for carbon dioxide, with a measurement time of 100 seconds. Selectivity was studied with a multicomponent gas mixture of propene, methane, carbon dioxide, and methylmercaptane. The results indicate that a quantitative analysis of all components in the mixture is possible using the FT-IR-PAS-OCD.

Effects of fatty acids on metabolism and cell growth of human colon cell lines of different transformation state.

Epidemiological studies suggest that high fish intake is associated with a decreased risk of colorectal cancer which has been linked to the high content of the n - 3 polyunsaturated fatty acids (PUFAs) eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in some fish. In this study, two different cell lines are compared in relation to their response to EPA and DHA versus the plant derived PUFAs, linoleic acid (LA), gamma-linolenic acid (GLA), and alpha-linolenic acid (ALA) and to the ubiquitous arachidonic acid (ARA). The uptake of 100 microM of each fatty acid (FA) was determined using GC. The 4',6-diamidino-2-phenylindole assay for DNA quantification and the Cell-Titer-Blue assay were used to determine cell survival and metabolic activity at 2-72 h after treatment. All FAs were utilized more efficiently by the human colon adenoma cell line LT97 than by the adenocarcinoma cell line HT29. LT97 were more susceptible than HT29 cells to the growth inhibitory activities of all FAs except for DHA where both were equally sensitive. Inhibition of survival and metabolic activity by EPA and DHA increased with treatment time in both cell lines. ALA or GLA were less growth inhibitory than EPA or DHA and ARA had intermediary activity. The data show that the tested FAs are incorporated into colon cells. Furthermore, adenoma cells are more susceptible than the adenocarcinoma cells.

Development of an analytical method for the unambiguous structure elucidation of cyclic peptides with special appliance for hepatotoxic desmethylated microcystins.

The periodical occurrence of harmful algal blooms (HABs) in freshwater lakes requires the determination of potential cyanobacterial toxins, especially microcystins (MCs). On demand of an adequate risk assessment, the high diversity of these hepatotoxic cyclic heptapeptides implicates the need of an unambiguous detection of their specific structural variants. Therefore, LC-MS and LC-MS/MS methods are the approaches of choice for determination of MCs. In contrast, even tandem mass spectromic fragmentation patterns are not even sufficient in any kind of structural determination requirements, whereas NMR methods require very high amounts of MCs. In this study, we present a novel method for chromatographic separation of desmethylated microcystins (dm-MCs). Based on the isolation of the specific structural variants using semi-preparative HPLC, a method was developed for the structure elucidation of cyclic peptides with special appliance for the determination of dm-MCs via analysis of the specific amino acid composition after peptide hydrolysis followed by stereospecific detection of the amino acids and resulting keto acids. On the basis of this method it is demonstrated that dm-MC-RR with the structure [Dha(7)]MC-RR represented the major compound in the microcystin pattern of Microcystis aeruginosa bloom events in 2005 and 2006 in Lake Senftenberg, Germany.

Are spirolides converted in biological systems?--A study.

Spirolides are biologically active macrocycles isolated first from scallops and phytoplankton from aquaculture sites in Nova Scotia, Canada. These compounds displayed "fast-acting" toxicity in the traditional bioassay. That phenomenon is related to the presence of a cyclic imine function in these compounds. Spirolides containing vicinal methyl groups in their seven-membered ring are suspected of being resistant to hydrolysis. We studied possible conversions of vicinal methyl groups wearing spirolides of Alexandrium ostenfeldii KO287 in enzymatic cell-free tissue extracts of Mytilus edulis, Pecten maximus and Crassostrea gigas. Our observations suggest that spirolides that contain an extra methyl group on the imine ring compared with spirolide A and B survive enzymatic hydrolysis conditions in shellfish and therefore may be toxic for human beings when shellfish is consumed.

Determination of marine biotoxins relevant for regulations: from the mouse bioassay to coupled LC-MS methods.

The frequency of occurrence and intensity of harmful algal blooms (HABs) appear to be increasing on a global scale. Consequently, methods were established for the evaluation of possible hazards caused by the enrichment of algal toxins in the marine food chain. Different clinical types of algae-related poisoning have attracted scientific attention: paralytic shellfish poisoning (PSP), diarrhetic shellfish poisoning (DSP), and amnesic shellfish poisoning (ASP). In several countries fish specialties are consumed which may be contaminated with algal toxins typical for the respective region (e.g., ciguatera and tetrodotoxins). Bioassays are common methods for the determination of marine biotoxins. However, biological tests are not completely satisfactory, due to the low sensitivity and the absence of specialized variations. Moreover, there is growing resistance against the use of animal experiments. Therefore, many efforts have been made to determine algal toxins with chemical methods. In this context LC-MS methods replaced HPLC methods with optical detectors, allowing both effective seafood control and monitoring of phytoplankton in terms of the different groups of marine biotoxins.

Determination of tetrodotoxin and its analogs in the puffer fish Takifugu oblongus from Bangladesh by hydrophilic interaction chromatography and mass-spectrometric detection.

Tetrodotoxin (TTX) and its analogs (TTXs), widely distributed among marine as well as terrestrial animals, induce dangerous intoxications. These highly potential toxins are also known as the causative agent of puffer fish poisoning. A newly developed highly sensitive method for determination of TTXs based on hydrophilic interaction chromatography and mass-spectrometric detection is presented. TTX, anhydrotetrodotoxin, 11-deoxytetrodotoxin and trideoxytetrodotoxin were determined in separated tissues of Bangladeshi marine puffers, Takifugu oblongus. TTX was predominant in skin, muscle and liver, whereas trideoxytetrodotoxin preponderated in the ovary. The toxicity of the various tissues was determined by a mouse bioassay.

Application of a new zwitterionic hydrophilic interaction chromatography column for determination of paralytic shellfish poisoning toxins.

A novel method for paralytic shellfish poisoning (PSP) toxins which is based on the chromatographic separation of the toxins using a zwitterionic (ZIC) hydrophilic interaction chromatography (HILIC) column is presented. Efficient retention of the polar PSP toxins on the ZIC-HILIC column allowed their selective and sensitive determination by the application of mass spectrometric (MS/MS) detection or as derivatives after oxidation prior to fluorescence detection (FD). Low buffer concentrations and the omission of ion-pair reagents decreased the limits of detection (LODs) by MS/MS analysis and showed a good linearity for both methods of detection. This method can be applied for the qualitative and quantitative determination of PSP toxins in various types of phytoplankton, and for the routine analysis of seafood.

Detection of harmful cyanobacteria and their toxins by both PCR amplification and LC-MS during a bloom event.

We briefly report here the occurrence of toxic blooms in the eutrophic reservoir Billings, São Paulo city, Brazil. Water samples were collected in May 2004, during a cyanobacterial bloom. The presence of toxic species was confirmed by using PCR amplifications of a fragment region of genes encoding microcystin synthetase-mcyB. The determination of toxins was performed by liquid chromatography coupled with mass spectrometry (LC-MS). LC-MS analyses of the toxins from the bloom revealed variants of microcystins (MC), such as MC-LR, MC-RR and MC-YR. HPLC-FLD was used to determine the paralytic shellfish poisoning (PSP) saxitoxin (STX), neosaxitoxin (NEO), gonyautoxins 2 (GTX2) and 3 (GTX3). GTX2, GTX3 and NEO were detected for the first time in a natural sample from Billings reservoir. These results are a contribution to the knowledge of the biogeography of toxic cyanobacteria and their toxins, specifically in São Paulo.