Determination of oryzalin in water, citrus fruits, and stone fruits by liquid chromatography with tandem mass spectrometry

A new methodology is described for rapidly determining the herbicide oryzalin in water, citrus fruits, and stone fruits by liquid chromatography with negative ion electrospray ionization tandem mass spectrometry (LC/MS/MS). Oryzalin is extracted from water using a polymeric sorbent solid phase extraction (SPE) column and from fruit using methanol. The water samples require no further purification, but an aliquot of the fruit sample extracts is diluted with water and purified using a polymeric 96 well SPE plate. Purified extracts are concentrated prior to determination by LC/MS/MS at m/z 345 (Q1) and m/z 281 (Q3) using an external standard for calibration. The validated limits of quantitation were 0.05 microg/L in water (drinking water, surface water, and groundwater) and 0.01 microg/g in citrus fruits (oranges and lemons) and stone fruits (peaches and cherries). Recoveries averaged 102% for water samples and 85-89% for the various types of fruit samples. For all fortification levels combined, the relative standard deviations ranged from 4 to 6% for water and from 2 to 4% for fruit.     

Carbohydrate composition of selected plum/prune preparations

Eighteen plum/prune preparations and byproducts were analyzed for proximate constituents and carbohydrate profiles. Plum puree and prune juice contained the highest concentrations of ash (13.0 and 13.8%, respectively). Crude protein (CP), acid-hydrolyzed fat (AHF), and total dietary fiber (TDF) concentrations were higher in byproducts (waste cake and dried plum pits) compared with the other fractions. Several classes of oligosaccharides were found in low concentrations in many of the substrates and were associated with the fruit rather than the pit. Maltooligosaccharides were found in very high concentrations in three of the preparations as a result of the addition of maltodextrin during processing. Monosaccharides, sugar alcohols, and oligosaccharides were found in higher concentrations in the fruit than in the pit and accounted for 2.9-84.7% of substrate organic matter. These results indicate that carbohydrates of various types constitute a significant proportion of plum/prune preparations and byproducts.     

Detection and characterization of DNA adducts formed from metabolites of the fungicide ortho-phenylphenol

The significance of DNA adduction in ortho-phenylphenol-induced carcinogenesis remains unclear. Establishing adduct structures may contribute to resolving this issue. The chemical structures of the DNA adduction products resulting from the in vitro reaction of phenylbenzoquinone, the putative ultimate carcinogenic metabolite of the fungicide/disinfectant ortho-phenylphenol, are reported here. Three isomeric adducts that resulted from reaction of deoxyguanosine were characterized by UV, LC-ESI-MS, and MS/MS, and 1D and 2D COSY-NMR spectroscopy. The proposed mechanism of product formation is nucleophilic attack by the deoxyguanosine exocyclic amine nitrogen on an electrophilic quinone carbon, followed by stabilization through enolization. Another nucleophilic attack forms a five-membered ring, which aromatizes by dehydration to form the final product. Adducts were also characterized from deoxyadenosine and deoxycytidine, although conversions were at least 10 times lower. Structures are also proposed for these products. Cell culture studies confirmed that HepG2 cells incubated with phenylbenzoquinone at concentrations associated with cytotoxicity form the same DNA adducts.     

Sheld-geese and man in the Falkland Islands

The history of the association between sheld-geese (upland geese Chloëphaga picta and ruddy-headed geese C. rubidiceps) and man in the Falkland Islands is described from the time when they were used as food by early settlers, to the conflict with the sheep industry. Geese were found to be extremely abundant when man first settled. A bounty scheme was instigated by sheep farmers in 1905 and claimed 74 000 geese annually between 1905 and 1912. Far fewer (25 000 annually) were killed in the late 1970s because fewer shepherds lived in the remote houses of sheep stations, and the bounty did not increase in proportion with wage increases. The population of geese remains large despite this toll and recent studies of the annual cycle, movements and population dynamics give reasons for the failure of the bounty scheme to reduce numbers. Information on food intake and densities of geese on different vegetation types has indicated that the geese populations take only 1·5% of the total annual organic matter production of herbage. This represents 7% of what is eaten by all the herbivores. However, most of this consumption is restricted to a few vegetation types with a relatively small area (e.g. ‘greens’ and reseeded pastures). It is the consumption from reseeds that causes the biggest problem to the sheep industry. Methods of control are discussed and the value of destruction of geese questioned.     

Applying combinatorial chemistry and biology to food research

In the past decade combinatorial chemistry has become a major focus of research activity in the pharmaceutical industry for accelerating the development of novel therapeutic compounds. The same combinatorial strategies could be applied to a broad spectrum of areas in agricultural and food research, including food safety and nutrition, development of product ingredients, and processing and conversion of natural products. In contrast to "rational design", the combinatorial approach relies on molecular diversity and high-throughput screening. The capability of exploring the structural and functional limits of a vast population of diverse chemical and biochemical molecules makes it possible to expedite the creation and isolation of compounds of desirable and useful properties. Several studies in recent years have demonstrated the utility of combinatorial methods for food research. These include the discovery of synthetic antimicrobial, antioxidative, and aflatoxin-binding peptides, the identification and analysis of unique flavor compounds, the generation of new enzyme inhibitors, the development of therapeutic antibodies for botulinum neurotoxins, the synthesis of unnatural polyketides and carotenoids, and the modification of food enzymes with novel properties. The results of such activities could open a large area of applications with potential benefits to the food industry. This review describes the current techniques of combinatorial chemistry and their applications, with emphasis on examples in food science research.     

Prioritization of ground water contaminants and sources

The objective of this research was to identify chemical, physical, bacteriological, and viral contaminants, and their sources, which present the greatest health threat in public ground water supplies in the USA; and to classify (prioritize) such contaminants and relative to their health concerns. The developed contaminant prioritization methodology was based on frequency of occurrence and adverse health effects. Adverse health effects were based on carcinogenic potency, toxicity, hazardous chemical priorities and drinking water standards. Application of the methodology for wellhead protection areas, (WHPAs) revealed that approximately 200 different contaminants have been detected in the nation's public ground water supplies. The seven chemical constituents with the highest priority were arsenic, chromium, cadmium, carbon tetrachloride, chloroform, 1, 1-dichloroethylene, and ethylene dibromide. Other contaminants of concern were trichloroethylene, nitrates, barium, 1,1,1-trichloroethane, benzene, tetrachloroethylene, selenium, lead, toluene, mercury, gross alpha radiation, methylene chloride, coliform bacteria, metolachlor, metribuzin, 1, 1, 2, 2-tetrachloroethane, dibromochloroethane, simazine, radium-266, and toxaphene. The contaminant source prioritization methodology was also based on frequency of occurrence. Over 30 categories of sources were evaluated, with the eight with highest priority including agricultural activities, hazardous waste sites, landfills, industrial operations, septic tank systems, oil and gas field activities, urban land use, and underground storage tanks.     

alpha-Naphthoflavone, a potent antiplatelet flavonoid, is mediated through inhibition of phospholipase C activity and stimulation of cyclic GMP formation

The aim of this study was to systematically examine the inhibitory mechanisms of the flavonoid alpha-naphthoflavone (alpha-NF) in platelet activation. In this study, alpha-NF concentration dependently (5-20 microM) inhibited platelet aggregation stimulated by agonists. alpha-NF (5 and 10 microM) inhibited intracellular Ca(2+) mobilization, phosphoinositide breakdown, and thromboxane A(2) formation stimulated by collagen (1 microg/mL) in human platelets. In addition, alpha-NF (5 and 10 microM) markedly increased levels of cyclic GMP and cyclic GMP-induced vasodilator-stimulated phosphoprotein (VASP) Ser(157) phosphorylation. Rapid phosphorylation of a platelet protein of Mr 47,000 (P47), a marker of protein kinase C activation, was triggered by phorbol-12,13-dibutyrate (60 nM). This phosphorylation was markedly inhibited by alpha-NF (5 and 10 microM). However, alpha-NF (5 and 10 microM) did not reduce the electron spin resonance (ESR) signal intensity of hydroxyl radicals in collagen (1 microg/mL)-activated platelets. These results indicate that the antiplatelet activity of alpha-NF may be involved in the following pathways. (1) alpha-NF may inhibit the activation of phospholipase C, followed by inhibition of phosphoinositide breakdown, protein kinase C activation, and thromboxane A(2) formation, thereby leading to inhibition of intracellular Ca(2+) mobilization. (2) alpha-NF also activated the formation of cyclic GMP, resulting in inhibition of platelet aggregation. These results strongly indicate that alpha-NF appears to represent a novel and potent antiplatelet agent for treatment of arterial thromboembolism.     

In-lake alkalinity generation by sulfate reduction: A paleolimnological assessment

The generation of alkalinity by SO₄ reduction and net storage of reduced S in lake sediments has been estimated from an analysis of sediment cores from 16 lakes in ME, VT, NY, MI, MN, and WY. The cores have been dated by ²¹⁰Pb. The rate of pre-1850 (background) storage of S in lake sediments suggests that alkalinity contribution to lake water from this process ranged from 0.2 to 9.3 geq L^?1, with an average of 4 geq L^?1, Background values are similar for all lakes and remain low in the WY lakes up to the present. Maximum alkalinity contributions recorded in sediment, from upper mid-west and eastern lakes, dated between 1850 and 1985 are between 0.4 and 33 geq L^?1, with a lake mean maximum of 9.9 geq L^?1, Significant increases in recent S storage only occur in eastern lakes. Average values for net S accumulation in the sediment of most lakes for post-1850 sediment are typically less than half of maximum values.     

Assessing selenium cycling and accumulation in aquatic ecosystems

We conducted a joint experimental research and modeling study to develop a methodology for assessing selenium (Se) toxicity in aquatic ecosystems. The first phase of the research focused on Se cycling and accumulation. In the laboratory, we measured the rates and mechanisms of accumulation, transformation, and food web transfer of the various chemical forms of Se that occur in freshwater ecosystems. Analytical developments helped define important Se forms. We investigated lower trophic levels (phytoplankton and bacteria) first before proceeding to experiments for each successive trophic component (invertebrates and fish). The lower trophic levels play critical roles in both the biogeochemical cycling and transfer of Se to upper trophic levels. The experimental research provided the scientific basis and rate parameters for a computer simulation model developed in conjunction with the experiments. The model includes components to predict the biogeochemical cycling of Se in the water column and sediments, as well as the accumulation and transformations that occur as Se moves through the food web. The modeled processes include biological uptake, transformation, excretion, and volatilization; oxidation and reduction reactions; adsorption; detrital cycling and decomposition processes; and various physical transport processes within the water body and between the water column and sediments. When applied to a Se-contaminated system (Hyco Reservoir), the model predicted Se dynamics and speciation consistent with existing measurements, and examined both the long-term fate of Se loadings and the major processes and fluxes driving its biogeochemical cycle.