Development and application of quantitative methods for monitoring dermal and inhalation exposure to propiconazole

Quantitative methods to measure dermal and inhalation exposure to the fungicide propiconazole were developed in the laboratory and applied in the occupational exposure setting for monitoring five farm workers' exposure during pesticide preparation and application to peach crops. Dermal exposure was measured with tape-strips applied to the skin, and the amount of propiconazole was normalized to keratin content in the tape-strip. Inhalation exposure was measured with an OVS tube placed in the worker's breathing-zone during pesticide handling. Samples were analyzed by GC-MS in EI+ mode (limit of detection 6 pg microl(-1)). Dermal exposure ranged from non-detectable to 32.1 +/- 22.6 ng per microg keratin while breathing-zone concentrations varied from 0.2 to 2.2 microg m(-3). A positive correlation was observed between breathing-zone concentrations and ambient air temperature (r2 = 0.87, p < 0.01). Breathing-zone concentrations did not correlate with dermal exposure levels (r2 = 0.11, p = 0.52). Propiconazole levels were below limit of detection when rubber gloves, coveralls, and full-face mask were used. The total-body propiconazole dose, determined for each worker by summing the estimated dermal dose and inhalation dose, ranged from 0.01 to 12 microg per kg body weight per day. Our results show that tape-stripping of the skin and the OVS can be effectively utilized to measure dermal and inhalation exposure to propiconazole, respectively, and that the dermal route of exposure contributed substantially more to the total dose than the inhalation route.     

Clinal variation in anuran advertisement calls: basis for acoustic isolation?

Summary The calls of male treefrogs (Eleutherodactylus coqui) were studied along an altitudinal gradient in the Luquillo Mountains in eastern Puerto Rico. The fundamental frequency of each note in the advertisement call was highly negatively correlated with altitude. Although males responded vigorously to playbacks of calls of other males recorded at their own altitude, males at high altitudes responded less frequently to recorded calls of males from low altitudes, and males at low altitudes responded less frequently to recorded calls of males from high altitudes. These results are discussed in relation to potential isolation in contiguous populations of E. coqui.     

Growth in otter (Lutra lutra) populations in the UK as shown by long-term monitoring

European otters declined dramatically from the 1950s, disappearing from many rivers. We report here on longterm monitoring (from 1977) in 3 catchments in western Britain that were recolonized naturally and in 2 catchments in eastern England that were reinforced by captive-bred otters. A minimum of 16-years data was collected on each river until 2002. At a series of sites in each study river, the percentages which were positive for otters and the number of spraints per sprainting site were recorded and combined to produce an annual index of population. One western river, naturally recolonized, showed rapid early population growth for 5 years, followed by slower growth, while growth was steadier in 2 catchments which already held some otters at the beginning of the study. Colonization on the eastern rivers was slower, with greater fluctuations over time. Annual population growth rates were estimated at 1-7%, higher in the earlier years. A strategy for annual monitoring of otters is recommended.     

Terpenylnaphthoquinones are reductively activated by NADH/NADH dehydrogenase

Novel terpenylnaphthoquinones were found to enhance the rate of oxygen consumption in the presence of NADH/NADH dehydrogenase in 1?:?1?v/v mixtures of 40?mM phosphate buffer (pH 7.4) and DMSO. Initial rates of oxygen consumption increase with an increase in the half-wave reduction potentials of the quinones. The amounts of spin trapped methyl radicals in the presence of DMSO, produced through the Haber–Weiss reaction of the oxygen consumption process, and of the corresponding semiquinones, generated under anaerobic conditions, also correlate with the quinone redox potential. Since this enzymatic system is found in mitochondria, a possible pathway in the cytotoxic activity of these terpenylnaphthoquinones could be the interference or inhibition of mitochondrial respiration by NADH depletion or by mitochondrial degradation due to reactive oxygen species generation.     

Heterologous expression of <Emphasis Type="Italic">LamA</Emphasis> gene encoded endo-β-1,3-glucanase and CO<Subscript>2</Subscript> fixation by bioengineered <Emphasis Type="Italic">Synechococcus</Emphasis> sp. PCC 7002

The gene for the catalytic domain of thermostable endo-β-1,3-glucanase (laminarinase) LamA was cloned from Thermotoga maritima MSB8 and heterologously expressed in a bioengineered Synechococcus sp. PCC 7002. The mutant strain was cultured in a photobioreactor to assess biomass yield, recombinant laminarinase activity, and CO₂ uptake. The maximum enzyme activity was observed at a pH of 8.0 and a temperature of 70°C. At a CO₂ concentration of 5%, we obtained a maximum specific growth rate of 0.083 h^–1, a biomass productivity of 0.42 g?L^–1?d^–1, a biomass concentration of 3.697 g?L^–1, and a specific enzyme activity of the mutant strain of 4.325 U?mg^–1 dry mass. All parameters decreased as CO₂ concentration increased from 5% to 10% and further to 15% CO₂, except enzyme activity, which increased from 5% to 10% CO₂. However, the mutant culture still grew at 15% CO₂ concentration, as reflected by the biomass productivity (0.26 g?L^–1?d^–1), biomass concentration (2.416 g?L^–1), and specific enzyme activity (3.247 U?mg^–1 dry mass).

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Factors affecting variability in the urinary biomarker 1,6-hexamethylene diamine in workers exposed to 1,6-hexamethylene diisocyanate

Although urinary 1,6-hexamethylene diamine (HDA) is a useful biomarker of exposure to 1,6-hexamethylene diisocyanate (HDI), a large degree of unexplained intra- and inter-individual variability exists between estimated HDI exposure and urine HDA levels. We investigated the effect of individual and workplace factors on urine HDA levels using quantitative dermal and inhalation exposure data derived from a survey of automotive spray painters exposed to HDI. Painters' dermal and breathing-zone HDI-exposures were monitored over an entire workday for up to three separate workdays, spaced approximately one month apart. One urine sample was collected before the start of work with HDI-containing paints, and multiple samples were collected throughout the workday. Using mixed effects multiple linear regression modeling, coverall use resulted in significantly lower HDA levels (p = 0.12), and weekday contributed to significant variability in HDA levels (p = 0.056). We also investigated differences in urine HDA levels stratified by dichotomous and classification covariates using analysis of variance. Use of coveralls (p = 0.05), respirator type worn (p = 0.06), smoker status (p = 0.12), paint-booth type (p = 0.02), and more than one painter at the shop (p = 0.10) were all found to significantly affect urine HDA levels adjusted for creatinine concentration. Coverall use remained significant (p = 0.10), even after adjusting for respirator type. These results indicate that the variation in urine HDA level is mainly due to workplace factors and that appropriate dermal and inhalation protection is required to prevent HDI exposure.