Wolfgang Kandler

Noble metals as permanent modifiers for the determination of mercury by electrothermal atomic absorption spectrometry

Palladium, gold, rhodium and iridium have been investigated as chemical modifiers for mercury determination by ETAAS. The gold/rhodium mixture and palladium alone, thermally reduced in the graphite tube, and also electrodeposited palladium give the best analytical performance. Under those conditions a characteristic mass of 110 pg is obtained for mercury. The amount and the reduction temperature of the modifier, together with the pyrolysis, atomization and cleaning temperatures for mercury have been optimized in order to find best conditions for permanent modification. Experimental conditions for palladium and rhodium after thermal and electrodeposition as a permanent modifier have also been optimized. It is shown that thermally deposited palladium can serve for about 50 firings when the maximum temperature does not exceed 1800°C. The tubes pretreated with a thermally deposited gold/rhodium mixture or electrodeposited palladium exhibit extended analytical lifetime (up to 500 firings without loss of sensitivity) even when tubes are heated up to 2000°C.

Fusarium toxins and total fungal biomass indicators in naturally contaminated wheat samples from north-eastern Poland in 2003

Concentrations of fungal metabolites were measured in 32 wheat grain samples from north-eastern Poland in 2003. The samples originated from fields cultivated conventionally (but varying in chemical protection level) or cultivated organically. Concentrations of Fusarium toxins (HT-2, DON, 3-AcDON, NIV), trichodiene, microbial biomass indicators (fungal ergosterol and general adenosine 5′-triphosphate (ATP)) and seed vigour were assessed. A large variation between samples was observed, depending on their origin. Seed from organic farms contained similar amounts of Fusarium toxins but more ergosterol and ATP than conventionally grown and chemically protected seed. The highest levels of toxins and ergosterol were detected in samples from conventional cultivation lacking chemical protection. Intensive agronomic practices (including complete chemical protection) significantly lowered the levels of ergosterol, ATP and trichodiene, as compared with other cultivation systems.

Atomic absorption spectrometric determination of mercury in soil standard reference material following microwave sample pretreatment

Several decomposition procedures and their influence on the determination of mercury by electrothermal (ET) and cold vapour (CV) atomic absorption spectrometry (AAS) have been studied. Soil samples were decomposed by microwave digestion in closed and open vessels as well as by digestion under reflux according to German standard. The use of different acids (HNO3, HCl or aqua regia) was evaluated and compared in respect to their influence on the determination of mercury by ET AAS and CV AAS. The digestion solutions were analyzed by ET AAS with a palladium modifier and by CV AAS using SnCl2 or NaBH4, as reducing agents. The detection limits obtained with different procedures were also evaluated. For the soil containing 6.25 μg/g of Hg the ET AAS measurements were possible. In the case of lower concentration of mercury the CV AAS determination following the microwave digestion procedure with HCl or aqua regia is recommended. The accuracy of the proposed procedure was confirmed by the determination of total mercury in SRM 2711 Montana Soil.

Mycotoxin profiles in the grain of Triticum monococcum, Triticum dicoccum and Triticum spelta after head infection with Fusarium culmorum

BACKGROUND The aim of study was to investigate mycotoxin profiles in the grain of spring lines of Triticum monococcum (12 lines), T. dicoccum (13 lines) and T. spelta (five lines), in comparison to the T. aestivum cultivar Sumai-3 which is resistant to Fusarium head blight. The grain was obtained from control heads and heads artificially inoculated in the field with Fusarium culmorum. Mycotoxins were determined by LC-MS/MS. RESULTS A total of 11 toxins were identified in control grain samples. Deoxynivalenol (DON) concentrations exceeded 0.5 mg kg(-1) in only three samples of T. monococcum grain and in one sample of T. dicoccum grain. Inoculation with F. culmorum resulted in a substantial increase in the concentrations of DON (to 63 mg kg(-1)) in the T. monococcum and DON-3-glucoside (to 5.6 mg kg(-1)) in the T. dicoccum. Inoculation contributed to a drop in tentoxin levels (by 57% in T. spelta) and to an increase of cyclodepsipeptide concentrations (in particular enniatins B and B(1)) being two-fold (T. monococcum) to four-fold (T. dicoccum) higher on average than in control samples. The Sumai-3 responded to inoculation with nearly a two-fold drop in the levels of the cyclodepsipeptides. CONCLUSION The results of a discriminant analysis for all identified toxins indicate that einkorn, emmer and spelt differ significantly with regard to the mycotoxin profiles of their grain.

Determination of measurement uncertainty for the determination of triazines in groundwater from validation data

Laboratories are increasingly urged to submit full uncertainties of their analytical results rather than only standard deviations. The determination of measurement uncertainties in compliance with the Guide to the Expression of Uncertainty in Measurement (GUM) is demonstrated using the validation approach explicitly endorsed by the recent edition of the EURACHEM guide for the determination of measurement uncertainty. Measurement uncertainty was split into uncertainty of the sample mass, uncertainty of the concentration of the stock standard solution, uncertainty of the calibration and uncertainty connected to within- and between-series precision. Uncertainties of sample mass and of the concentration of the stock standard solution were 0.26 and 1.14% for all analytes, which is negligible compared with the contributions of precision and calibration. Uncertainty of calibration was estimated from the calibration graph. Relative uncertainty of calibration was found to be strongly concentration dependent and to be the main uncertainty contribution below 0.2 microgram L-1. Precision was split into within-series and between-series standard deviation, which dominate the combined standard uncertainty at higher concentrations. The results obtained from these calculations are compared with results for a certified reference material and with the performance in an interlaboratory comparison. It was found that all results agreed within their uncertainty with the target values, showing that the estimated uncertainties are realistic.

Evidence of In Vivo Absorption of Lactate and Modulation of Short Chain Fatty Acid Absorption from the Reticulorumen of Non-Lactating Cattle Fed High Concentrate Diets

Short-chain fatty acids (SCFAs) and lactate are endproducts of rumen fermentation and important energy sources for the host ruminant. Because their rapid accumulation results in ruminal acidosis, enhancement of the absorption of SCFA and lactate across reticuloruminal wall is instrumental in increasing energy supply and preventing ruminal acidosis in cattle. This study investigated whether the reticuloruminal absorption of SCFAs and lactate was altered by different strategies of high concentrate feeding. Eight rumen-cannulated, non-lactating Holstein cows were fed a forage-only diet (baseline) and then gradually adapted over 6 d to a 60% concentrate level. Thereafter, this concentrate-rich diet was fed for 4 wk either continuously (Con; n = 8) or interruptedly (Int; n = 8). Absorption of SCFAs and lactate was determined in vivo from the experimental buffer introduced into the washed reticulorumen. The buffer contained acetate, propionate, butyrate and lactate at a concentration of 60, 30, 10 and 5 mmol/L, respectively and Cr-EDTA as a marker for correcting ruminal water fluxes. The reticuloruminal absorption after 35 and 65 min of buffer incubation was measured at the baseline, after 1 wk of 60% concentrate feeding in the interrupted model (Int-1) and after 4 wk of concentrate feeding in both feeding models (Int-4 and Con-4). Data showed that the absorption rates of individual and total SCFAs during the first 35 min of incubation of Con-4 were highest (~1.7 times compared to baseline), while Int-1 and Int-4 were similar to respective baseline. Lactate was not absorbed during forage-only baseline and 1-wk concentrate feeding, but after 4-wk feeding of concentrates in both models. In conclusion, SCFAs absorption across the reticulorumen of non-lactating cattle was enhanced by the 4-wk continuous concentrate feeding, which seems to be more advantageous in terms of rumen acidosis prevention compared to the interrupted feeding model. The study provides evidence of lactate absorption across the reticulorumen of non-lactating cattle after both continuous and interrupted 4-wk concentrate feeding.

Concentrations of Some Metabolites Produced by Fungi of the Genus Fusarium and Selected Elements in Spring Spelt Grain

ABSTRACT The aim of this study was to determine the content of selected elements and metabolites produced by fungi of the genus Fusarium in spelt (Triticum spelta L.) grain and husks and common wheat (T. aestivum L.) grain. Concentrations of trichothecenes, a volatile metabolite trichodiene (TRICH), as well as ergosterol (ERG) and adenosine 5′-triphosphate (ATP) (a total microbial biomass indicator), were assessed. Toxin concentrations in spelt grain and husks harvested in 2003 and 2004 were comparable. Average deoxynivalenol concentrations reached 450 and 523 μg/kg in grain and 2,162 and 855 μg/kg in husks, respectively. Spelt grain, in comparison with common wheat grain, contained significantly higher concentrations of P, S, Mg, Zn, and Cu and a lower concentration of Al, whereas the concentrations of Ca, Fe, and Pb were significantly higher in the husks than in the grain of this cereal. A comparison of concentrations of Fusarium spp. metabolites in the grain of spelt and common wheat showed that the to...

Influence of high inorganic selenium and manganese diets for fattening pigs on oxidative stability and pork quality parameters.

Data are scarce regarding combined high Se and Mn supplementation in livestock diets, however, as Se and Mn are functionally related as cofactors of glutathione peroxidase (GPx) and Mn-superoxide dismutase (SOD), respectively, beneficial synergistic effects on oxidative stability of tissues may result. This experiment evaluated the effect of an oversupply of Se and Mn within European legal limits compared with recommendations on performance, oxidative stability of the organism and meat quality in a randomised complete block design. A total of 60 crossbred gilts were fed maize-barley-soya bean meal diets formulated in a 2×2 factorial approach with inorganic Se (0.2 v. 0.5 mg/kg Se dry matter (DM)) or inorganic Mn (20 v. 150 mg/kg Mn DM) from 31 to 116 kg BW. Se supplementation reduced feed intake, whereas high Mn diets impaired average daily gain (P<0.05). Qualitative carcass characteristics were impaired by Se and Mn predominantly in the semimembranosus muscle. Activity of GPx in liver was increased by high Se diets (P<0.05). Mn supplementation increased catalase (CAT) activity in liver, GPx in plasma and total antioxidative capacity (TAC) in muscle, whereas it decreased CAT activity in plasma (P<0.05). Cu/Zn-SOD in muscle showed higher activity in high-Se-low-Mn diets but lower activity when both high Se and Mn were combined (Se×Mn P<0.05). Mn supplementation increased Mn concentration in longissimus thoracis et lumborum, but simultaneously reduced Se concentration (P<0.05). Upon retail display, Mn increased lipid oxidation more pronouncedly (higher thiobarbituric acid reactive substances; P<0.05) than Se (P<0.10). Despite some positive effects (Mn increased TAC, Se increased GPx, Se and Mn increased tenderness), no synergistic effects of high Se and Mn diets or an overall beneficial impact on meat quality, especially during storage, could be observed. Including the negative effects on performance, feeding Se and Mn up to the maximum legal level cannot be recommended.

Fourier transform infrared - attenuated total reflection for wheat grain**

Fourier transform infrared - attenuated total reflection for wheat grain Mid-infrared regions of the spectrum of grain of four Triticum species were analyzed using Fourier transform infrared - attenuated total reflection. Significant variations were noted in the absorbance of all studied taxa over four wavenumber ranges. The principal component analysis supported strong discrimination of the four examined species. The percentage of variation explained by the first two principal component analyses reached 95.04%, including principal components 1-72.16% and 2-22.88%. The applied method supports quick identification of the grains of various hulled species of wheat and it is a useful tool for evaluating the seeds and food products obtained from those cereal species.

Enzymatically Modified Starch Favorably Modulated Intestinal Transit Time and Hindgut Fermentation in Growing Pigs.

Aside from being used as stabilizing agents in many processed foods, chemically modified starches may act as functional dietary ingredients. Therefore, development of chemically modified starches that are less digestible in the upper intestinal segments and promote fermentation in the hindgut receives considerable attention. This study aimed to investigate the impact of an enzymatically modified starch (EMS) on nutrient flow, passage rate, and bacterial activity at ileal and post-ileal level. Eight ileal-cannulated growing pigs were fed 2 diets containing 72% purified starch (EMS or waxy cornstarch as control) in a cross-over design for 10 d, followed by a 4-d collection of feces and 2-d collection of ileal digesta. On d 17, solid and liquid phase markers were added to the diet to determine ileal digesta flow for 8 h after feeding. Reduced small intestinal digestion after the consumption of the EMS diet was indicated by a 10%-increase in ileal flow and fecal excretion of dry matter and energy compared to the control diet (P<0.05). Moreover, EMS feeding reduced ileal transit time of both liquid and solid fractions compared to the control diet (P<0.05). The greater substrate flow to the large intestine with the EMS diet increased the concentrations of total and individual short-chain fatty acids (SCFA) in feces (P<0.05). Total bacterial 16S rRNA gene abundance was not affected by diet, whereas the relative abundance of the Lactobacillus group decreased (P<0.01) by 50% and of Enterobacteriaceae tended (P<0.1) to increase by 20% in ileal digesta with the EMS diet compared to the control diet. In conclusion, EMS appears to resemble a slowly digestible starch by reducing intestinal transit and increasing SCFA in the distal large intestine.