Analysis of veterinary drugs and metabolites in milk using quadrupole time-of-flight liquid chromatography-mass spectrometry

A quadrupole time-of-flight (Q-TOF) liquid chromatography-mass spectrometry (LC-MS) method was developed to analyze veterinary drug residues in milk. Milk samples were extracted with acetonitrile. A molecular weight cutoff filter was the only cleanup step in the procedure. Initially, a set of target compounds (including representative sulfonamides, tetracyclines, β-lactams, and macrolides) was used for validation. Screening of residues was accomplished by collecting TOF (MS(1)) data and comparing the accurate mass and retention times of found compounds to a database containing information for veterinary drugs. The residues included in the study could be detected in samples fortified at the levels of concern with this procedure 97% of the time. Although the method was intended to be qualitative, an evaluation of the MS data indicated a linear response and acceptable recoveries for a majority of target compounds. In addition, MS/MS data were also generated for the [M + H](+) ions. Product ions for each compound were identified, and their mass accuracy was compared to theoretical values. Finally, incurred milk samples from cows dosed with veterinary drugs, including sulfamethazine, flunixin, cephapirin, or enrofloxacin, were analyzed with Q-TOF LC-MS. In addition to monitoring for the parent residues, several metabolites were detected in these samples by TOF. Proposed identification of these residues could be made by evaluating the MS and MS/MS data. For example, several plausible metabolites of enrofloxacin, some not previously observed in milk, are reported in this study.     

Ovicidal and adulticidal activity of Eucalyptus globulus leaf oil terpenoids against Pediculus humanus capitis (Anoplura: Pediculidae)

The toxic effects of Eucalyptus globulus leaf oil-derived monoterpenoids [1,8-cineole, l-phellandrene, (-)-alpha-pinene, 2-beta-pinene, trans-pinocarveol, gamma-terpinene, and 1-alpha-terpineol] and the known Eucalyptusleaf oil terpenoids (beta-eudesmol and geranyl acetate) on eggs and females of the human head louse, Pediculus humanus capitis, were examined using direct contact and fumigation bioassays and compared with the lethal activity of delta-phenothrin and pyrethrum, two commonly used pediculicides. In a filter paper contact bioassay with female P. h. capitis, the pediculicidal activity was more pronounced with Eucalyptus leaf oil than with either delta-phenothrin or pyrethrum on the basis of LT(50) values (0.125 vs 0.25 mg/cm(2)). 1,8-Cineole was 2.2- and 2.3-fold more toxic than either delta-phenothrin or pyrethrum, respectively. The pediculicidal activities of (-)-alpha-pinene, 2-beta-pinene, and (E)-pinocarveol were comparable to those of delta-phenothrin and pyrethrum. l-Phellandrene, gamma-terpinene, and 1-alpha-terpineol were relatively less active than delta-phenothrin and pyrethrum. beta-Eudesmol and geranyl acetate were ineffective. 1-alpha-Terpineol and (E)-pinocaveol were highly effective at 0.5 and 1.0 mg/cm(2), respectively, against P. h. capitis eggs. At 1.0 mg/cm(2), (-)-alpha-pinene, 2-beta-pinene, and gamma-terpinene exhibited moderate ovicidal activity, whereas little or no ovicidal activity was observed with the other terpenoids and with delta-phenothrin and pyrethrum. In fumigation tests with female P. h. capitis at 0.25 mg/cm(2), 1,8-cineole, (-)-alpha-pinene, (E)-pinocarveol, and 1-alpha-terpineol were more effective in closed cups than in open ones, indicating that the effect of the monoterpenoids was largely due to action in the vapor phase. Neither delta-phenothrin nor pyrethrum exhibited fumigant toxicity. Eucalyptus leaf oil, particularly 1,8-cineole, 1-alpha-terpineol, and (E)-pinocaveol, merits further study as potential pediculicides or lead compounds for the control of P. h. capitis.     

Chemical comparison of goldenseal (Hydrastis canadensis L.) root powder from three commercial suppliers

The characterization of herbal materials is a significant challenge to analytical chemists. Goldenseal (Hydrastis canadensis L.), which has been chosen for toxicity evaluation by NIEHS, is among the top 15 herbal supplements currently on the market and contains a complex mixture of indigenous components ranging from carbohydrates and amino acids to isoquinoline alkaloids. One key component of herbal supplement production is botanical authentication, which is also recommended prior to initiation of efficacy or toxicological studies. To evaluate material available to consumers, goldenseal root powder was obtained from three commercial suppliers and a strategy was developed for characterization and comparison that included Soxhlet extraction, HPLC, GC-MS, and LC-MS analyses. HPLC was used to determine the weight percentages of the goldenseal alkaloids berberine, hydrastine, and canadine in the various extract residues. Palmatine, an isoquinoline alkaloid native to Coptis spp. and other common goldenseal adulterants, was also quantitated using HPLC. GC-MS was used to identify non-alkaloid constituents in goldenseal root powder, whereas LC-MS was used to identify alkaloid components. After review of the characterization data, it was determined that alkaloid content was the best biomarker for goldenseal. A 20-min ambient extraction method for the determination of alkaloid content was also developed and used to analyze the commercial material. All three lots of purchased material contained goldenseal alkaloids hydrastinine, berberastine, tetrahydroberberastine, canadaline, berberine, hydrastine, and canadine. Material from a single supplier also contained palmatine, coptisine, and jatrorrhizine, thus indicating that the material was not pure goldenseal. Comparative data for three commercial sources of goldenseal root powder are presented.     

Influence of salinity in irrigation water on forage sorghum and soil chemical properties

Abstract

Soluble salts found in wastewater can be toxic when used for irrigation of forages. Thus, two greenhouse experiments were conducted to investigate effects of saline [CaCl₂NaCl (3:1, w:w)] treatments on soil chemical properties and ‘Dekalb FS‐5’ forage sorghum [Sorghum bicolor(L.) Moench]. Treatments for the first experiment consisted of a nonsaline control or 500 mL of a solution with an electrical conductivity (EC) of 10 dS m^?1 applied once. In the second experiment, treatments were salinity levels of 1.7,3.5,5.2,8.5, and 12.2 dS m^?1, applied in non‐nitrogenous Hoagland's solution as the sole source of irrigation. Both experiments were replicated four times. For both experiments forage sorghum was seeded in pots containing 7 kg of air‐dried Amarillo fine sandy loam soil. Sorghum survivability and plant height were measured. In the second experiment, water use by sorghum was also measured. Plants were harvested 7 wk after seeding, weighed, dried at 55°C, weighed, and ground for subsequent mineral analysis. After harvest, soil salinity, pH, and in the second experiment, extractable soil elements were determined. Soil salinity increased, while soil pH decreased, with the salinity treatments. Extracted soil calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), manganese (Mn), and cadmium (Cd) increased while sulfur (S), iron (Fe), and copper (Cu) decreased, and aluminum (Al) and zinc (Zn) exhibited no change with increasing salinity. Sorghum aerial plant and root production decreased with increasing salinity. Plant Ca, strontium (Sr), Mn, and Cd levels increased with increasing salinity. In contrast, sorghum K, P, and S levels declined with increasing salinity.     

Enhancement of Protein Foam Stability by Formation of Wheat Arabinoxylan-Protein Crosslinks

The foam stability properties of a defined mixed solution of Tween 20 and bovine serum albumin was evaluated as a function of arabinoxylan concentration. A marked increase in the foam stability was observed with low concentrations of arabinoxylan. Maximum improvement in the foam stability was obtained with 0.2–0.3 mg/mL of arabinoxylan. Enhancement of foam stability due to a combination of bulk viscosity changes and surface effects was identified. The relative contribution of arabinoxylan to bulk viscosity and adsorbed layer structure was studied by examination of the properties of thin liquid films and the macroscopic air-water interface. Arabinoxylan reduced the rate of thin film drainage, increased the equilibrium thickness of the films, slowed the lateral diffusion of a fluorescent probe molecule located in the adsorbed layer, and increased the surface elasticity. These data are congruent with arabinoxylan-mediated crosslinking of adsorbed protein. These observations may be of significance in gas retention during breadmaking. In addition, this naturally occurring polysaccharide offers potential for use in the control of protein foam stability.     

Nitrate/ammonium ratio effects on mineral element uptake by sorghum 1

Abstract

Experiments were conducted using different NO₃ ^–/NH₄ ⁺ ratios to determine the effects of these sources of N on mineral element uptake by sorghum [Sorghum bicolor (L.) Moench] plants grown in nutrient solution. The NO₃ ^–/NH₄ ⁺ ratios in nutrient solution were 200/0, 195/5, 190/10, and 160/40 mg N L^–1. Nutrient solutions were sampled daily and plants harvested every other day during the 12‐day treatment period.

Moderately severe Fe deficiencies were observed on leaves of plants grown with 200/0 NO₃ ^–/NH₄ ⁺ solutions, but not on the leaves of plants grown with the other NO₃ ^–/NH₄ ⁺ ratios. As plants aged, less Fe, Mn, and Cu were translocated from the roots to leaves and leaf/root ratios of these elements decreased dramatically in plants grown with 200/0 NO₃ ^–/NH₄ ⁺ solutions. Extensive amounts of Fe, Mn, and Cu accumulated in or on the roots of plants grown with 200/0 NO₃ ^–/NH₄ ⁺ solutions. Manganese and Cu may have interacted strongly with Fe to inhibit Fe translocation to leaves and to induce Fe deficiency. As the proportion of NH₄ ⁺ in solution increased, K, Ca, Mg, Mn, and Zn concentrations decreased in the leaves, and Ca, Mg, Mn, and Cu concentrations decreased in roots. Potassium and Zn tended to increase in roots as NH₄ ⁺ in solution increased.     

Adverse effects of simulated harvesting of short-rotation willow and poplar coppice on vertical pressures and rut depths

Little is known of the effects of mechanized harvesting on ground conditions during the harvesting of short-rotation coppice. An investigation was therefore carried out in which different vehicles were used to simulate the effects of wheeling from heavy and light harvesters and crop removal equipment. The experiments were carried out on sites containing Bowles hybrid willow (Salix viminalis) and poplars (Populas rap) and on clay and sandy loam soils. The effect of different vehicles was assessed in terms of rut damage and direct measurements of soil stress using buried sensors. Maximum stresses measured 0.3 m below tractor wheels ranged from 50 to 200 kPa, but the greatest stresses, 350 kPa, were recorded under laden trailer wheels. Maximum stresses measured beneath crawler tracks were only 25 kPa. Similarly, substantial ruts were caused by vehicles simulating wheeled harvesters, the deepest ruts were caused by laden trailers but crawler tracks created least disturbance. Wheeling was carried out at soil water contents above the plastic limit and the deepest ruts were created on clay rather than sandy loam soil. The effects of the stresses generated in the soil could impede future root growth, and the deeper ruts formed could damage existing root systems of coppice.     

Environmental nitroso compounds: reaction of nitrite with creatine and creatinine

Creatine reacts with nitrite under acid conditions to produce first sarcosine and then N-nitrososarcosine, which is a weak carcinogen in the rat. Creatinine reacts with acidified nitrite to produce either creatinine-5-oxime or 1-methylhydantoin-5-oxime, depending on reaction conditions. The toxicity and environmental significance of these compounds is not yet known.     

Field Scale Mapping of Surface Soil Clay Concentration

The surface soil clay concentration is a useful soil property to map soils, interpret soil properties, and guide irrigation, fertilizer, and agricultural chemical applications. The objective of this study was to determine whether surface soil clay concentrations could be predicted from remotely sensed imagery of bare surface soil or from soil electrical conductivity for a 115 ha field located in Crisp County, Georgia. The soil clay concentrations were determined for soil samples taken at 28 field locations. Three different data sources–an aerial color photograph image, two infrared bands from an ATLAS data set, and the electrical conductivity of the surface soil layer were used in the research. Principal components analysis was applied to the color photograph image, whereas the ratio of two infrared bands was applied to the ATLAS data set. Filtering was applied to both resulting images. The distribution of soil electrical conductivity was derived from the measured soil electrical conductivity data by spatial analysis. Statistical relationships between soil clay concentrations and the principal component 3, the ratio of two ATLAS infrared bands, and the soil electrical conductivity were analyzed, and three linear equations were derived with r ² values 0.83, 0.52, and 0.78, respectively. The distribution of the soil clay concentrations was derived based on these three equations. Six levels of soil clay concentrations were classified in these three methods, and the advantages and disadvantages were discussed. The predicted and measured soil clay concentrations, based on additional soil samples from 30 field locations, were compared using linear regression (r ²=0.76, 0.45, and 0.77 for the three methods). The overall accuracy for these methods were 84%, 66%, and 76%, respectively. The principal components method had the highest accuracy in our research, while the result for the depressional areas is the best from the ratio method.