Chemical-sensory characterization of dairy manure odor using headspace solid-phase microextraction and multidimensional gas chromatography mass spectrometry-olfactometry

Livestock operations are associated with emissions of odor, gases, and particulate matter. The majority of previous livestock odor studies focused on swine operations whereas relatively few relate to dairy cattle. Identifying the compounds responsible for the primary odor impact is a demanding analytical challenge because many critical odor components are frequently present at very low concentrations within a complex matrix of numerous insignificant volatiles. The objective of this study was to describe a chemical-sensory profile of dairy manure odor using headspace solid-phase microextraction (HS-SPME) and multidimensional gas chromatography-mass spectrometry-olfactometry (MDGC-MS-O). Two analytical approaches were used: (1) HS-SPME time-series extractions (from seconds up to 20 hr) followed by gas chromatography-mass spectrometry-olfactometry (GC-MS-O) analyses, and (2) relatively short HS-SPME extractions (30 min) followed by MDGC-MS-O analyses on selected chromatogram heart-cuts. Dairy manure was collected at research dairy farms in the United States and Israel. Volatile organic compounds (VOCs) resolved from multiple analyses included sulfur-containing compounds, volatile fatty acids, ketones, esters, and phenol/indole derivatives. A total of 86 potential odorants were identified. Of them, 17 compounds were detected by the human nose only. A greater number of VOCs and odorous compounds were detected, as well as higher mass loading, on solid-phase microextraction (SPME) fibers observed for longer extractions with SPME. However, besides sulfur-containing compounds, other selected compounds showed no apparent competition and displacement on the SPME fiber. The use of MDGC-MS-O increased chromatographic resolution even at relatively short extractions and revealed 22 additional odorants in one of the regions of the chromatogram. The two analytical approaches were found to be parallel to some extent whereas MDGC-MS-O can also be considered as a complementary approach by resolving more detailed chemical-sensory odor profiles.     

Biomagnification of mercury in trophic relation of Great Cormorant (Phalacrocorax carbo) and fish in the Vistula Lagoon, Poland

Total mercury (Hg) concentrations were determined by CV-AAS in selected tissues (liver, kidney, and muscle) of the Great Cormorant and some fish species (herring, ruffe, European smelt, tench, roach, Crucian carp, and Prussian carp) from the Vistula Lagoon ecosystem (Poland). Significant correlations between Hg concentrations in the kidneys and muscle of cormorants (U test, p?<?0.05) were found; levels of the metal were highest in the birds?? liver and kidneys. Total Hg concentrations in the fish decreased in the following order: roach > Prussian carp > Crucian carp > tench > European smelt > ruffe > herring. The biomagnification factor of Hg for the cormorant relative to the fish decreased in the following sequence: herring > ruffe > European smelt > tench > Crucian carp > roach = Prussian carp. It was significantly greater than unity, especially for the cormorant?Cherring trophic relationship. This implies that Hg is biomagnified in the cormorant in relation to its prey.     

Degradation of bisphenol A using UV and UV/H2O2 processes

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol) is a substance typically used in the plastic industry. It is used in the production of epoxy resins, polycarbonate, or fire retardants or as a stabilizer and an antioxidant in numerous types of plastics. Bisphenol A is introduced into the environment via municipal and industrial wastewater. Because of its hydrophobic properties, BPA has the potential for sorption on activated sludge during the biological wastewater treatment processes. This study investigated the degradation of BPA by means of UV-radiation and in the UV/H2O2 process with the presence and absence of hydrocarbonate ions (HCO3(-)) as hydroxyl radicals (OH*) scavengers. The calculated value of quantum yield was equal to 0.18, and the value of BPA rate constant with hydroxyl radicals was equal to 3.3 x 10(9) M(-1) s(-1).     

Cadmium,lead and mercury concentrations in pathologically altered human kidneys

Heavy metals, including cadmium (Cd), lead (Pb) and mercury (Hg) act as nephrotoxic agents, particularly in the renal cortex. The aim of the study was to determine the concentrations of Cd, Pb and Hg in kidneys removed from patients due to lesions of various etiologies and from patients after the rejection of transplanted kidneys. Additionally, we determined the influence of selected biological and environmental factors on the concentrations of toxic metals. The study material consisted of kidneys with tumor lesions (n = 27), without tumors (n = 7) and its extracted grafts (n = 10) obtained from patients belongs to the north-western areas of Poland. The determined metal concentrations in the renal cortex and medulla may be arranged in the following descending order: Cd > Pb > Hg. The highest concentrations of Cd and Hg were found in the cortex, while the maximum content Pb was observed in the medulla. Significant correlations were found in the concentrations of the same metals between cortex and medulla and between Pb and Hg in the renal medulla. Pb content was higher in the renal medulla of men than in the cortex of the elderly (above 60 years of age). The highest concentrations of Pb and Hg were found in the cortex and medulla, of the kidneys had not neoplastic changes, and lower content of these metals were found in the extracted kidney grafts. In summary, renal grafts accumulate less heavy metals than cancerous kidneys, what could have been caused by immunosuppressors taken by the graft recipients. Moreover, sex, age and smoking are key factors responsible for xenobiotics concentrations.     

Application of physicochemical data for water-quality assessment of watercourses in the Gdansk Municipality (South Baltic coast)

The paper presents water-quality evaluation based on an 8-year monitoring programme in the Gdansk Municipality region, on the Southern coast of the Baltic Sea. The studies were carried out from 2000 to 2007 by surface water analysis at 15 various sites within eight watercourses. Sampling sites included rather urbanized or developed lands, farming fields and non-polluted city recreational areas such as parks and forests. Most of the watercourses were sampled monthly at two locations, one within the upper course of the watercourse and the other near its mouth. In all samples, eight parameters of water quality were determined: total suspended solids, dissolved oxygen, water temperature, oxygen saturation, 5-day biochemical oxygen demand, chemical oxygen demand, total phosphorus and total nitrogen concentration. Interpretation of the obtained results revealed that examination of those basic physicochemical parameters permits to discriminate initially watercourses with respect to level of water contamination. During the research, a large dataset was obtained and it was described by both basic statistical parameters and chemometric method of cluster analysis. The paper presents relations between analysed parameters and influence of land exploitation mode on water quality and describes variation of the results both in space and time.     

The content of butyl- and phenyltin derivatives in the sediment from the Port of Gdansk

Harbor sediments containing large deposits of organotin compounds constitute a potential threat to the marine environment. Samples of harbor sediments were collected twice in the years 2003 and 2005 from the following locations: Zió?kowskiego, Siarkowe, Wi?lane, Weglowe, Chemików and Paliw P?ynnych Quays. The cores of 25cm length sliced into 2- and 5-cm segments were analyzed. After drying and homogenization, samples were split into two granulometric fractions, i.e. <2.00 and <0.063mm. The dominant fraction in whole sediment, i.e. fraction grain diameter <2.00mm, was sand (grain diameter 2.00-0.063mm). However, the highest concentrations of butyltin (BT) and phenyltin (PT) compounds were found in the fine sediment fraction. The mean values of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) in the analyzed samples in the <2.00mm fraction were 2144.9, 434.7 and 148.1ngSng(-1)d.w., respectively, while the corresponding mean values in the <0.063mm fraction were 6556.4, 1593.7 and 450.0ngSng(-1)d.w. The mean concentrations of monophenyltin (MPhT) have been estimated at 29.0 and 49.9ngSng(-1)d.w. for the <2.00 and <0.063mm fraction sizes, respectively. The estimated content levels of diphenyltin (DPhT) and triphenyltin (TPhT) were in most cases below the detection limit of the applied method. The sediment cores collected from the locations characterized by high industrialization and intense exploitation (Wi?lane, Weglowe Quays) contained the highest concentrations of BT and PT.     

Characterization of livestock odors using steel plates, solid-phase microextraction, and multidimensional gas chromatography-mass spectrometry-olfactometry

Livestock operations are associated with emissions of odor, gases, and particulate matter (PM). Livestock odor characterization is one of the most challenging analytical tasks. This is because odor-causing gases are often present at very low concentrations in a complex matrix of less important or irrelevant gases. The objective of this project was to develop a set of characteristic reference odors from a swine barn in Iowa and, in the process, identify compounds causing characteristic swine odor. Odor samples were collected using a novel sampling methodology consisting of clean steel plates exposed inside and around the swine barn for < or =1 week. Steel plates were then transported to the laboratory and stored in clean jars. Headspace solid-phase microextraction was used to extract characteristic odorants collected on the plates. All of the analyses were conducted on a gas chromatography-mass spectrometry-olfactometry system where the human nose is used as a detector simultaneously with chemical analysis via mass spectrometry. Multidimensional chromatography was used to isolate and identify chemicals with high-characteristic swine odor. The effects of sampling time, distance from a source, and the presence of PM on the abundance of specific gases, odor intensity, and odor character were tested. Steel plates were effectively able to collect key volatile compounds and odorants. The abundance of specific gases and odor was amplified when plates collected PM. The results of this research indicate that PM is major carrier of odor and several key swine odorants. Three odor panelists were consistent in identifying p-cresol as closely resembling characteristic swine odor, as well as attributing to p-cresol the largest odor response out of the samples. Further research is warranted to determine how the control of PM emissions from swine housing could affect odor emissions.     

Changes in mussel Mytilus galloprovincialis protein profile as a reaction of water pollution

In the present report the changes in mussels Mytilus galloprovincialis protein profile, as a reaction of water pollution, is presented. The antioxidant capacity was determined by the efficacy to scavenge the derived radical in mussel samples using the Trolox Equivalent Antioxidant Capacity (TEAC) assay. The highest percentage of inhibition was estimated in protein mussels from the dirty area (DM) in comparison with the clean samples (CM). The amounts of both zinc and copper determined by atomic spectroscopy were significantly higher in the protein mussels from the dirty than from the clean areas (P<0.05). Fourier Transform Infrared (FT-IR) spectroscopy and fluorescence revealed specific qualitative changes in secondary and tertiary structures of mussel proteins from the dirty area by the shift in the amides I and II positions and fluorescence intensity. Estimated temperature and enthalpy of denaturation in the protein mussels well correlated with fluorescence and spectroscopic measurements and showed the changes influenced by water pollution.     

Overexpression of LCT1 in tobacco enhances the protective action of calcium against cadmium toxicity

Wheat cDNA LCT1, a nonspecific transporter for Ca2+, Cd2+, Na+ and K+, was overexpressed in tobacco. Transformants were tested for their sensitivity to a range of Ca2+-concentrations [0.01-10 mM Ca(NO3)2] with or without the presence of 0.05 mM Cd(NO3)2. Calcium and cadmium accumulation was also determined. LCT1-transformed plants expressed a phenotype distinct from controls only under conditions of low calcium (0.01-1 mM Ca2+). They grew significantly better and had slightly higher shoot calcium concentration. Transformants subjected to 0.05 mM Cd(NO3)2 in the presence of 1 mM Ca2+ displayed a substantially higher level of tolerance to cadmium and accumulated less Cd in roots. These results are the first to demonstrate the involvement of LCT1 in calcium acquisition and in the regulation of amelioration of Cd-toxicity by calcium.     

Solid State Reactions of Potato Starch with Urea and Biuret

Reaction of granular potato starch with urea and biuret resulted in the formation of products, which were soluble neither in cold nor boiling water. The net reaction was a monosubstitution of the hydrogen atom in one hydroxyl group in each D-glucose unit of starch with the either CO–NH₂ or CO–NH–CO–NH₂ moiety, respectively. Properties of the products, particularly these with urea, depended on the mode of reaction. Reactions were carried out in the microwave oven as well as with convection heating. The products retained the granular form of starch but a vast majority of granules were damaged. -Amylolysis of those materials revealed that their susceptibility to the enzyme increasing in the order: starch-amylolysis with simultaneous insolubility in water make these products suitable as ruminant fodder and, eventually, biodegradable material.