MULTIPLE FORMS OF α-AMYLASE IN MALTING BARLEY VAR. EMMA.

Multiple forms of α-amylase arise from translation of separate messages and post-translational proteolytic modification during malting. α-amylase activity is tolerant of proteolysis. The enzyme appears to have two domains one of which is associated with starch cleavage. The second site which binds cyclodextrin is destroyed by proteolysis. Cleavage yields a low molecular weight form which retains α-amylase activity.     

Molecular studies to identify the Fusarium species responsible for HT-2 and T-2 mycotoxins in UK oats

High levels of Fusarium mycotoxins HT-2 and T-2 have been detected in UK oats since surveys started in 2002. Fusarium langsethiae and the closely related species F. sporotrichioides have previously been associated with the contamination of cereals with type A trichothecenes HT-2 and T-2 in Nordic countries. Preliminary microbiological analysis of UK oat samples with high concentrations of HT-2 and T-2 detected and isolated F. langsethiae and F. poae but not the other type A trichothecene producing species F. sporotrichioides, F. sibiricum and F. armeniacum. Two hundred and forty oat flour samples with a known mycotoxin profile were selected from a previous four year study (2002-2005) to cover the full concentration range from below the limit of quantification (<20 μg/kg) to 9,990 μg/kg HT-2+T-2 combined. All samples were analysed for the DNA of F. langsethiae, F. poae and F. sporotrichioides based on previously published PCR assays. F. langsethiae was detectable in nearly all samples; F. poae was detected in 90% of samples whereas F. sporotrichioides was not detected in any sample. A real-time PCR assay was developed to quantify F. langsethiae DNA in plant material. The assay could quantify as low as 10(-4)ngF. langsethiae DNA/μl. Based on this assay and a previously published assay for F. poae, both species were quantified in the oat flour samples with known HT-2+T-2 content. Results showed a good regression (P<0.001, r(2)=0.60) between F. langsethiae DNA and HT-2+T-2 concentration. F. poae DNA concentration was not correlated to HT2+T2 concentration (P=0.448) but was weakly correlated to nivalenol concentration (P<0.001, r(2)=0.09). Multiple regression with F. langsethiae and F. poae DNA as explanatory variates identified that both F. langsethiae and F. poae DNA were highly significant (P<0.001) but F. poae DNA only accounted for an additional 4% of the variance and the estimate was negative, indicating that higher concentrations of F. poae DNA were correlated with slightly lower concentrations of HT2+T2 detected. A stronger regression (P<0.001, r(2)=0.77) between F. langsethiae DNA and HT-2+T-2 was obtained after extraction and quantification of DNA and mycotoxins from individual oat grains. The results from this study provide strong evidence that F. langsethiae is the primary, if not sole, fungus responsible for high HT-2 and T-2 in UK oats.     

Estrogenic activity and steroid hormones in swine wastewater through a lagoon constructed-wetland system

Anaerobic lagoons and treatment wetlands are used worldwide to treat wastewater from dense livestock production facilities; however, there is very limited data on the hormonal activity of the wastewater effluent produced by these treatment systems. The objectives of this experiment were to measure (1) the hormonal activity of the initial effluent and (2) the effectiveness of a lagoon-constructed wetland treatment system for producing an effluent with a low hormonal activity. Wastewater samples were taken in April, July, and November 2004 and July 2005 from a lagoon-constructed wetland system at a swine farrowing facility. Estrogenic activity (in vitro E-screen assay), 17 beta-estradiol (E2), and testosterone concentrations (LC/MS-MS) were measured. A high correlation was found between estradiol equivalents determined by E-screen and LC/MS-MS (R2 = 0.82). Nutrient removal was measured to ensure that the wetlands were functioning in a manner similar to literature reports. Nutrient removals were typical for treatment wetlands: TKN 59-75% and orthophosphate 0-18%. Wetlands decreased estrogenic activity by 83-93%. Estrone was the most persistent estrogenic compound. Constructed wetlands produced effluents with estrogenic activity below the lowest equivalent E2 concentration known to have an effect on fish (10 ng/L or approximately 37 x 10(-12) M).     

Formation of chloroform and other chlorinated byproducts by chlorination of triclosan-containing antibacterial products

Triclosan is a widely used antibacterial agent found in many personal hygiene products. Although it has previously been established that pure triclosan and free chlorine readily react, interactions between triclosan-containing consumer products and free chlorine have not previously been analyzed in great depth. Sixteen double-blinded solutions including both triclosan-containing (1.14-3.12 mg triclosan/g product) and triclosan-free products were contacted with free chlorine at pH 7. Products detected included (chlorophenoxy) phenols, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and chloroform. The daughter product yields were found to be highly variable and were dependent on the antimicrobial product investigated, the free chlorine to triclosan ratio, and the temperature at which the study was conducted. Lowering the temperature from 40 to 30 degrees C resulted in a decreased average chloroform yield from 0.50 to 0.37 mol chloroform/mol triclosan consumed after 1 min of reaction time for an initial free chlorine concentration of 4.0 mg/L as Cl2. At 40 degrees C the average molar chloroform yields decreased to 0.29 and <0.1 when the initial free chlorine concentration was decreased to either 2.0 or 1.0 mg/L as Cl2, respectively. Field experiments, in which Atlanta, GA and Danville, VA tap waters were augmented with various soap products, exhibited results varying from the laboratory experiments in that different productyields were observed. These differences are attributed to the chlorine demand of constituents in the tap water. A simple exposure model suggests that exposure to chloroform can be significant under some conditions.     

Long-term stability of organic carbon-stimulated chromate reduction in contaminated soils and its relation to manganese redox status

In situ reduction of toxic Cr(VI) to less hazardous Cr(III) is becoming a popular strategy for remediating contaminated soils. However, the long-term stability of reduced Cr remains to be understood, especially given the common presence of Mn(III, IV) oxides that re-oxidize Cr(III). This 4.6 year laboratory study tracked Cr and Mn redox transformations in soils contaminated with Cr(VI), which were then treated with different amounts of organic carbon (OC). Changes in Cr and Mn oxidation states within soils were directly and nondestructively measured using micro-X-ray absorption near-edge structure spectroscopy. Chromate reduction was roughly first-order, and the extent of reduction was enhanced with higher OC additions. However, significant Cr(III) re-oxidation occurred in soils exposed to the highest Cr(VI) concentrations (2560 mg kg(-1)). Transient Cr(Ill) re-oxidation up to 420 mg kg(-1) was measured at 1.1 years after OC treatment, followed by further reduction. Chromate concentrations increased by 220 mg kg(-1) at the end of the study (4.6 years) in one soil. The causal role that the Mn oxidation state had in re-oxidizing Cr was supported by trends in Mn K-edge energies. These results provide strong evidence for long-term dependence of soil Cr oxidation states on balances between OC availability and Mn redox status.     

Do increases in cigarette prices lead to increases in sales of cigarettes with high tar and nicotine yields?

We used scanner data on cigarette prices and sales collected from supermarkets across the United States from 1994 to 2004 to test the hypothesis that cigarette prices are positively correlated with sales of cigarettes with higher tar and nicotine content. During this period the average inflation-adjusted price for menthol cigarettes increased 55.8%. Price elasticities from multivariate regression models suggest that this price increase led to an increase of 1.73% in sales-weighted average tar yields and a 1.28% increase in sales-weighted average nicotine yields for menthol cigarettes. The 50.5% price increase of nonmenthol varieties over the same period yielded an estimated increase of 1% in tar per cigarette but no statistically significant increase in nicotine yields. An ordered probit model of the impact of cigarette prices on cigarette strength (ultra-light, light, full flavor, unfiltered) offers an explanation: As cigarette prices increase, the probability that stronger cigarette types will be sold increases. This effect is larger for menthol than for nonmenthol cigarettes. Our results are consistent with earlier population-based cross-sectional and longitudinal studies showing that higher cigarette prices and taxes are associated with increasing consumption of higher-yield cigarettes by smokers.     

Effect of UV irradiation on organic matter extracted from treated Ohio River water studied through the use of electrospray mass spectrometry

Ohio River water was treated by settling, sand filtration, and granular activated carbon filtration. It was then irradiated by low-pressure (monochromatic) and medium-pressure (polychromatic) UV lamps to investigate the effects of UV irradiation on the extracted organic matter (EOM). When the EOM, collected by solid phase extraction cartridges, was analyzed by conventional UV spectroscopy and size exclusion chromatography (SEC), no significant changes in the EOM were revealed for various UV doses. Positive and negative electrospray ionization mass spectrometry (ESI-MS) of the EOM produced mass spectra that vary significantly with UV dose. The UV dosage conditions also appear to affect the reactivity of the EOM to subsequent chlorination. The magnitude of the spectral changes is generally greater for medium-pressure lamps than for low pressure and increases with UV exposure. Based on the observed MS peaks, the changes may be due to the presence of lignin, resulting perhaps from photooxidation and/or photo rearrangement of macromolecules in the sample. When chlorination is used for secondary disinfection, these results suggest that it may be important to consider the effects of UV irradiation on the organic matter in the water before applying UV disinfection technology to a particular source water.     

Atmospheric mercury in the Lake Michigan basin: influence of the Chicago/Gary urban area

The relative importance of the Chicago/Gay urban area was investigated to determine its impact on atmospheric mercury (Hg) concentrations and wet deposition in the Lake Michigan basin. Event wet-only precipitation, total particulate, and vapor phase samples were collected for Hg, and trace element determinations from five sites around Lake Michigan from July 1994 through October 1995 as part of the Lake Michigan Mass Balance Study (LMMBS). In addition, intensive over-water measurements were conducted aboard the EPA research vessel Lake Guardian during the summer of 1994 and the winter of 1995 as part of the Atmospheric Exchange Over Lakes and Oceans Study. Atmospheric Hg concentrations were found to be significantly higher in the Chicago/Gary urban area than surrounding sites: Hg in precipitation was a factor of 2 and particulate Hg was a factor of 6 times higher. Overwater measurements found elevated Hg concentrations 19 km off shore of Chicago/Gary suggesting an enhanced near field atmospheric deposition to Lake Michigan. Meteorological transport analyses also determined that local sources in the Chicago/Gary urban area significantly impacted all of the LMMBS sites indicating a broad impact to the entire Lake Michigan basin.     

Source reconciliation of atmospheric gas-phase and particle-phase pollutants during a severe photochemical smog episode

A comprehensive organic compound-based receptor model is developed that can simultaneously apportion the source contributions to atmospheric gas-phase organic compounds, semivolatile organic compounds, fine particle organic compounds, and fine particle mass. The model is applied to ambient data collected at four sites in the south coast region of California during a severe summertime photochemical smog episode, where the model determines the direct primary contributions to atmospheric pollutants from 11 distinct air pollution source types. The 11 sources included in the model are gasoline-powered motor vehicle exhaust, diesel engine exhaust, whole gasoline vapors, gasoline headspace vapors, organic solvent vapors, whole diesel fuel, paved road dust, tire wear debris, meat cooking exhaust, natural gas leakage, and vegetative detritus. Gasoline engine exhaust plus whole gasoline vapors are the predominant sources of volatile organic gases, while gasoline and diesel engine exhaust plus diesel fuel vapors dominate the emissions of semivolatile organic compounds from these sources during the episode studied at all four air monitoring sites. The atmospheric fine particle organic compound mass was composed of noticeable contributions from gasoline-powered motor vehicle exhaust, diesel engine exhaust, meat cooking, and paved road dust with smaller but quantifiable contributions from vegetative detritus and tire wear debris. In addition, secondary organic aerosol, which is formed from the low-vapor pressure products of gas-phase chemical reactions, is found to be a major source of fine particle organic compound mass under the severe photochemical smog conditions studied here. The concentrations of secondary organic aerosol calculated in the present study are compared with previous fine particle source apportionment results for less intense photochemical smog conditions. It is shown that estimated secondary organic aerosol concentrations correlate fairly well with the concentrations of 1,2-benzenedicarboxylic acid in the atmospheric fine particle mass, indicating that aromatic diacids may be useful in the quantification of certain sources of secondary organic aerosol in the atmosphere.     

Discrimination of aerial deposition sources of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran downwind from a pulp mill near Ketchikan, Alaska

Drinking water is supplied by individual roof-catchment systems for homes and businesses near a dissolving sulfite pulp mill (now closed) located just north of Ketchikan in southeast Alaska. This study was conducted to determine if polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) found in the sediments of the roof-catchment cisterns resulted from historical deposition of stack emissions from the pulp mill's multi-fuel power boilers. Fly ash from the power boilers had maximum total PCDD/F concentrations of 3.08 x 10(5)-3.10 x 10(6) ng/kg, which resulted from combustion of bleach plant wastewater sludge and saltwater-soaked wood waste. Cistern sediments had maximum total PCDD/F concentrations of 7.71 x 10(4) ng/kg. Potential sources of PCDDs/Fs in the cistern sediments were considered to be automobile exhaust, heating oil combustion, and private trash burning as well as pulp mill boiler emissions. Discriminant analysis was used to analyze differences between profiles of tetra through octa homologue classes of PCDDs/ Fs (defined as proportional contributions to total concentration) from different source terms. Homologue profiles of potential sources from Ketchikan included in this analysis were fly ash collected from the mill's power boilers and soils collected from background areas (areas with similar PCDD/F sources as the residences [e.g., auto exhaust and burn barrels] near the mill but beyond the zone of aerial deposition of emissions from the mill). Profiles for emissions from automobile exhaust, fertilizers, oil heating, residential trash burning, and residential wood heating were also included in the source "training" data set (for the discriminant analysis) using data from published literature. The classification rules developed from the discriminant analysis were applied to the following test media sampled at Ketchikan: roof-catchment cistern sediments and soils collected from areas in the vicinity of the mill's power boilers (i.e., nearby residential or commercial [developed] areas, on the mill property, and nearby forestlands). The homologue profiles of cistern sediment and nearby developed area soil samples were similar to background soils, whereas the profiles for the forestland soil samples (influenced by emissions from the mill but not other anthropogenic sources) closely matched the fly ash pattern. The homologue profiles of the emission sources from published data were more similar to one another than either background soils or fly ash. Soil samples from the mill property were classified as members of all source groups. On the basis of these analyses, the composition of PCDDs/Fs detected in the cistern sediments is typical of Ketchikan background conditions and not reflective of mill emissions.