Toxicological properties of thio- and alkylphenols causing flavor tainting in fish from the upper Wisconsin River

EC50 Microtox (5 min, 25 degrees C) assay values for 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2,4-diisopropylphenol, 2,5-diisopropylphenol 2,6-diisopropylphenol, 3,5-diisopropylphenol, carvacrol, thymol, thiophenol, and thiocresol ranged from 2 x 10(-2) mM for thymol (least toxic) to 2 x 10(-4) mM for 2,4-diisopropylphenol and 4-isopropylphenol (most toxic).     

Environmental and industrial factors relating to flavor tainting of fish in the upper Wisconsin river

Extracts from Large Toothed Aspen (Populous grandidenta Michx.) and Jack Pine (Pinus banksiana Lamb.) contained many odor compounds found in flavor-tainted walleye from the Wisconsin River, including alkylphenols. Aspen wood contained 8 ppb of 2-isopropylphenol, and river sediments also contained low ppb levels of many alkylphenols, including 2-isopropylphenol. Thiophenol and thiocresol which sporadically cause offensive sulfury taints in Wisconsin River fish were also found in river sediment. Quantitative analysis of fish for alkylphenols supported a hypothesis involving a food chain-mediated seasonal fluctuation of alkylphenol levels in fish. Thiophenols are postulated to be derived from pulp mill activities on the river.     

Photodegradation mechanism for bisphenol A at the TiO2/H2O interfaces

Bisphenol A (BPA) can be decomposed photocatalytically under UV-illumination in aqueous TiO2 dispersion. The two methyl groups in BPA were initially attacked with .OH and/or .OOH radicals having strong oxidizing power, followed by the cleavage of the two phenyl moieties. Finally, the photomineralization to CO2 gas occurred via oxidative processes involving carboxylic acids and aldehydes. The decomposition of structurally similar substances of 4,4'-ethylidenebisphenol (EBP) and 4,4'-methylenebisphenol (MBP) was compared. The decomposition of BPA gave more kinds of intermediates such as 4-isopropylphenol, 4-ethylphenol, etc. On the other hand, that of EBP gave mainly 4-isopropylphenol and that of MBP gave a predominant product of 4-hydroxybenzaldehyde. These photooxidative pathways were proposed on the base of the evidence of oxidative intermediate formation.     

Variability in the content and composition of alkaloid found in Canadian ergot. iii. triticale and barley∗

Abstract

The total alkaloid content and individual alkaloid composition were determined by colorimetry and high performance liquid chromatography, respectively, for Canadian triticale and barley ergot (Claviceps purpurea). The total alkaloid content was highly variable between individual sclerotia from the same or different sources and ranged from 0.042 to 0.752% for triticale and from 0.082 to 1.04% for barley; average values were 0.239% for Ottawa triticale, 0.289% for Prairie triticale, and 0.264% for barley. Ergocristine and its isomer ergocristinine were the major constituents in both grains. On average, Canadian ergot pooled from rye, wheat, triticale, and barley consists of ergocristine (31%), ergocristinine (13%), ergocristinine (13%), ergotamine (17%), ergotaminine (8%), ergocryptine (5%), ergocryptinine (3%), ergo‐metrine (5%), ergometrinine (2%), ergosine (4%), ergosinine (2%), ergocornine (4%), ergocorninine (2%), and unidentified alkaloids (3%) and an average total alkaloid content of 0.236%. With the exception of rye and barley ergot from the maritime regions, Canadian rye, wheat, triticale, and barley ergot is fairly uniform in individual alkaloid composition.     

Spatial soil zinc content distribution from terrain parameters: A GIS-based decision-tree model in Lebanon

Heavy metal contamination has been and continues to be a worldwide phenomenon that has attracted a great deal of attention from governments and regulatory bodies. In this context, our study proposes a regression-tree model to predict the concentration level of zinc in the soils of northern Lebanon (as a case study of Mediterranean landscapes) under a GIS environment. The developed tree-model explained 88% of variance in zinc concentration using pH (100% in relative importance), surroundings of waste areas (90%), proximity to roads (80%), nearness to cities (50%), distance to drainage line (25%), lithology (24%), land cover/use (14%), slope gradient (10%), conductivity (7%), soil type (7%), organic matter (5%), and soil depth (5%). The overall accuracy of the quantitative zinc map produced (at 1:50.000 scale) was estimated to be 78%. The proposed tree model is relatively simple and may also be applied to other areas.     

Comparison of source apportionments of fine particulate matter at two San Jose speciation trends network sites

In this study, the chemical composition of fine particulate matter samples collected at U.S. Environmental Protection Agency Speciation Trends Network sites in San Jose, CA, from February 2000 to February 2005 were analyzed. A San Jose site was initially established at 4th Street and then subsequently moved to Jackson Street in mid-2002. These sites are approximately 1 km apart. There were no known major changes in the nature of the sources in the area over this period. The study used positive matrix factorization model to extract the source profiles and their mass contributions and to compare the results for the congruence of the source apportionments between these two nearby sites. In the case of the 4th Street site, the average mass was apportioned to wood combustion (32.1 +/- 2.5%), secondary nitrate (22.3 +/- 2%), secondary sulfate (10.7 +/- 0.6%), fresh sea salt (7.7 +/- 0.9%), gasoline vehicles (7.3 +/- 0.5%), aged sea salt (6.8 +/- 0.4%), road dust (6.7 +/- 0.7%), diesel emissions (3.9 +/- 0.3%), and a Ni-related industrial source (2.5 +/- 0.4%). At the Jackson Street site, the average mass was apportioned to wood combustion (33.6 +/- 2.6%), secondary nitrate (20.3 +/- 1.9%), secondary sulfate (13.9 +/- 0.9%), aged sea salt (12.4 +/- 0.7%), gasoline vehicle (8.3 +/- 0.6%), fresh sea salt (5.3 +/- 0.5%), diesel emission (3.2 +/- 0.3%), road dust (1.9 +/- 0.1%), and Ni-related industrial source (1.3 +/- 0.1%). Conditional probability function analysis was used to help identify local sources. These results suggested that moving the sampling site a short distance had little effect on the nature of the resolved source types although some differences in their quantitative impacts were obtained in the positive matrix factorization analyses.     

Seasonal performance of an outdoor constructed wetland for graywater treatment in a temperate climate

The seasonal treatment efficiency of a pilot-scale constructed wetland system located outdoors in a semi-arid, temperate climate was evaluated for graywater in a comprehensive, 1-year study. The system consisted of two wetland beds in series--a free water surface bed followed by a subsurface flow bed. Water quality monitoring evaluated organics, solids, nutrients, microbials, and surfactants. The results showed that the wetland substantially reduced graywater constituents during fall, spring, and summer, including biochemical oxygen demand (BOD) (92%), total nitrogen (85%), total phosphorus (78%), total suspended solids (TSS) (73%), linear alkylbenzene sulfonate (LAS) surfactants (94%), and E. coli (1.7 orders of magnitude). Except for TSS, lower removals of graywater constituents were noted in winter--BOD (78%), total nitrogen (64%), total phosphorus (65%), LAS (87%), and E. coli (1.0 order), indicating that, although wetland treatment slowed during the winter, the system remained active, even when the average water temperature was 5.2 +/- 4.5 degrees C.     

Dietary exposure to PCBs based on food consumption survey and food basket analysis at Taizhou, China--the world's major site for recycling transformers

The levels of PCBs in different types of food (fish, shellfish, meat, rice, vegetables, and fruits) were analyzed to determine the dietary intake of 37 PCBs for local residents and e-waste workers (all lactating mothers) at Taizhou (China), a major electronic waste scrapping center, in particular for recycling transformers. The exposure to PCBs through dietary intake in Taizhou was estimated at 92.79 ngkg(-1)d(-1), contributed by consumption of freshwater fish (28%), rice (28%), meat (17%), shellfish (9%), vegetables (8%), egg (4%) and marine fish (2%). With regards to WHO-PCB-TEQ values, freshwater fish (40%), shellfish (24%), duck liver (18%) and rice (12%) were the main dietary sources with total daily intake (9.78 pg WHO-PCB-TEQ kg(-1)d(-1)), exceeding the FAO/WHO Tolerable Daily Intake (70 pg TEQkg(-1)body(-1)wt(-1)month(-1)).     

Biological treatment of wastewater by selected aquatic plants

Pollutant-removal efficiency of certain macrophytes and algae, such as Eichhornia crassipes, Microcystis aeruginosa, Scenedesmus falcatus, Chlorella vulgaris and Chlamydomonas mirabilis, has been tested in laboratory conditions to evaluate their potential role in wastewater treatment. Sewage of Varanasi city, mixed with the effluents of about 1200 small-scale industries, was used for the tests. The investigation was performed in three stages i.e. a water hyacinth culture followed by an algal culture, and finally a second water hyacinth culture. For the first water hyacinth culture, 10 water hyacinth plants were grown in a tank of wastewater with 15 days' retention time. In the second stage, algal species were cultured in the treated wastewater for 5 days, whilst in the third stage, water hyacinth plants were again grown for further treatment of the wastewater for 9 days. This three-stage aquaculture resulted in very high reductions of BOD (96.9%), suspended solids (78.1%), total alkalinity (74.6%), PO(4)-P (89.2%), NO(3)-N (81.7%), acidity (73.3%), NH(4)-N (95.1%), COD (77.9%), hardness (68.6%) and coliform bacteria (99.2%). An increase in the concentration of dissolved oxygen (70%) was also observed.     

Source apportionment of VOCs in the Los Angeles area using positive matrix factorization

Eight 3-h speciated hydrocarbon measurements were collected daily by the South Coast Air Quality Management District (SCAQMD) as part of the Photochemical Assessment Monitoring Stations (PAMS) program during the summers of 2001–03 at two sites in the Los Angeles air basin, Azusa and Hawthorne. Over 30 hydrocarbons from over 500 samples at Azusa and 600 samples at Hawthorne were subsequently analyzed using the multivariate receptor model positive matrix factorization (PMF). At Azusa and Hawthorne, five and six factors were identified, respectively, with a good comparison between predicted and measured mass. At Azusa, evaporative emissions (a median of 31% of the total mass), motor vehicle exhaust (22%), liquid/unburned gasoline (27%), coatings (17%), and biogenic emissions (3%) factors were identified. Factors identified at Hawthorne were evaporative emissions (a median of 34% of the total mass), motor vehicle exhaust (24%), industrial process losses (15%), natural gas (13%), liquid/unburned gasoline (13%), and biogenic emissions (1%). Together, the median contribution from mobile source-related factors (exhaust, evaporative emissions, and liquid/unburned gasoline) was 80% and 71% at Azusa and Hawthorne, respectively, similar to previous source apportionment results using the chemical mass balance (CMB) model. There is a difference in the distribution among mobile source factors compared to the CMB work, with an increase in the contribution from evaporative emissions, though the cause (changes in emissions or differences between models) is unknown.     

Source identification of atlanta aerosol by positive matrix factorization

Data characterizing daily integrated particulate matter (PM) samples collected at the Jefferson Street monitoring site in Atlanta, GA, were analyzed through the application of a bilinear positive matrix factorization (PMF) model. A total of 662 samples and 26 variables were used for fine particle (particles < or = 2.5 microm in aerodynamic diameter) samples (PM2.5), and 685 samples and 15 variables were used for coarse particle (particles between 2.5 and 10 microm in aerodynamic diameter) samples (PM10-2.5). Measured PM mass concentrations and compositional data were used as independent variables. To obtain the quantitative contributions for each source, the factors were normalized using PMF-apportioned mass concentrations. For fine particle data, eight sources were identified: SO4(2-) -rich secondary aerosol (56%), motor vehicle (22%), wood smoke (11%), NO(3-) -rich secondary aerosol (7%), mixed source of cement kiln and organic carbon (OC) (2%), airborne soil (1%), metal recycling facility (0.5%), and mixed source of bus station and metal processing (0.3%). The SO4(2-) -rich and NO(3-) -rich secondary aerosols were associated with NH(4+). The SO4(2-) -rich secondary aerosols also included OC. For the coarse particle data, five sources contributed to the observed mass: airborne soil (60%), NO(3-)-rich secondary aerosol (16%), SO4(2-) -rich secondary aerosol (12%), cement kiln (11%), and metal recycling facility (1%). Conditional probability functions were computed using surface wind data and identified mass contributions from each source. The results of this analysis agreed well with the locations of known local point sources.     

The disposition and metabolism of 1,3-dibromobenzene in the rat

The distribution, excretion and metabolism of 1,3-dibromobenzene following a single i.p. administration to rats 100 or 300 mg/kg was investigated using radiotracer [3H] and GC-MS technique. After 72 hours about 74 to 90% were excreted in urine. The highest radioactivity was observed in the liver, kidneys and fat tissue. Later on a steady decline of radioactivity was apparent in all investigated tissues except for blood cells and the sciatic nerve, where constant levels were noted. In urine the following substances were identified and quantified by GC peak areas: unchanged 1,3-DBB (18%), dibromophenols (34%), dibromothiophenols (28%), dibromothioanisole (1.8%), bromophenol (5.5%), bromohydroxythiophenols (5%), and bromohydroxythioanisole (7.5%).     

Effects of some insecticides on several enzymes of tryptophan metabolism in rats

The activities of tryptophan 2,3-dioxygenase (EC 1.13.11.11), indoleamine 2,3-dioxygenase (EC 1.13.11.17), kynurenine 3-hydroxylase (EC 1.14.13.9), kynureninase (EC 3.7.1.3), kynurenine transaminases, and pyridoxal phosphokinase (EC 2.7.1.35) in the liver, kidney and lung rats were measured after administration of a single dose and repeated doses of dimethoate, carbaryl and fenvalerate, respectively. Ten percent LD50 of each insecticide was orally administered to a rat for a single dose, while 5% LD50 was orally given for five consecutive days as repeated doses. The control animals received the same volume of vehicle (polyethylene glycol 300). Body weight and organs weight losses were recognized only after repeated doses of dimethoate, while protein content remained constant compared to control animals. Repeated administration of dimethoate caused significant decrease in the activity of kynurenine 3-hydroxylase (28.3% decrease in liver, and 32.5% in kidney), kynurenine-pyruvate transaminase (EC 2.6.1.7) (40% in liver, and 24.2% in kidney), kynurenine- pyruvate transaminase (EC 2.6.1-) (24.5% in kidney) and pyridoxal phosphokinase (36.1% in liver). Repeated doses of carbaryl resulted in a significant decrease in the activity of apo-tryptophan 2,3-dioxygenase (42.8%), kynurenine-2-oxoglutarate transaminase (40% in liver), kynurenine-pyruvate transaminase (30.6% in liver), and serine-glyoxylate transaminase (EC 2.6.1.51) (47.9% in liver). Externally added insecticides at different concentrations to the incubation mixture resulted in an inhibition to tryptophan 2,3-dioxygenase, while the other enzymes examined showed no change in their activities.     

A new alternative fuel for reduction of polycyclic aromatic hydrocarbon and particulate matter emissions from diesel engines

This study investigated the emissions of polycyclic aromatic hydrocarbons (PAHs), carcinogenic potential of PAH and particulate matter (PM), brake-specific fuel consumption (BSFC), and power from diesel engines under transient cycle testing of six test fuels: premium diesel fuel (PDF), B100 (100% palm biodiesel), B20 (20% palm biodiesel + 80% PDF), BP9505 (95% paraffinic fuel + 5% palm biodiesel), BP8020 (80% paraffinic fuel + 20% palm biodiesel), and BP100 (100% paraffinic fuel; Table 1). Experimental results indicated that B100, BP9505, BP8020, and BP100 were much safer when stored than PDF. However, we must use additives so that B100 and BP100 will not gel as quickly in a cold zone. Using B100, BP9505, and BP8020 instead of PDF reduced PM, THC, and CO emissions dramatically but increased CO2 slightly because of more complete combustion. The CO2-increased fraction of BP9505 was the lowest among test blends. Furthermore, using B100, B20, BP9505, and BP8020 as alternative fuels reduced total PAHs and total benzo[a]pyrene equivalent concentration (total BaPeq) emissions significantly. BP9505 had the lowest decreased fractions of power and torque and increased fraction of BSFC. These experimental results implied that BP9505 is feasible for traveling diesel vehicles. Moreover, paraffinic fuel will likely be a new alternative fuel in the future. Using BP9505 instead of PDF decreased PM (22.8%), THC (13.4%), CO (25.3%), total PAHs (88.9%), and total BaPeq (88.1%) emissions significantly.     

Metabolism of the environmental estrogen bisphenol A by plant cell suspension cultures

The metabolism of the environmental estrogen bisphenol A (BPA) was studied in heterotrophic plant cell suspension cultures of soybean (Glycine max), wheat (Triticum aestivum), foxglove (Digitalis purpurea), and thorn apple (Datura stramonium), which were regarded as metabolic model systems for intact plants. Three main metabolic routes of BPA were observed in the tissues. Most of the radioactivity found in the cell extracts consisted of carbohydrate conjugates of BPA amounting to about 85% (foxglove), 80% (wheat), 7% (soybean) and 15% (thorn apple) of applied 14C. The second main route was formation of non-extractable residues. Portions detected were low in foxglove (3.9% of applied 14C), moderate in wheat (13.5%), high in thorn apple (27.4%) and soybean (49.4%). With thorn apple, BPA derived bound residues were preponderantly resistant towards acid treatment; only traces of BPA were released. The third route was the formation of a highly polar, presumably polymeric material detected in media of soybean and thorn apple (29.3% and 36.0% of applied 14C, respectively). The mechanism of its formation remained unknown. In thorn apple, this highly polar material was formed extremely rapidly, and was considerably stable. Only traces of BPA were liberated by hydrolytic treatment with cellulase or acid. During hydrolysis experiments with glycoside fractions, non-extractable residues and highly polar materials, low amounts of presumably primary metabolites of BPA (up to 6% of applied 14C) were detected besides the parent compound; their chemical structures remained unclear.     

A New Alternative Fuel for Reduction of Polycyclic Aromatic Hydrocarbon and Particulate Matter Emissions from Diesel Engines

Abstract

This study investigated the emissions of polycyclic aromatic hydrocarbons (PAHs), carcinogenic potential of PAH and particulate matter (PM), brake-specific fuel consumption (BSFC), and power from diesel engines under transient cycle testing of six test fuels: premium diesel fuel (PDF), B100 (100% palm biodiesel), B20 (20% palm biodiesel + 80% PDF), BP9505 (95% paraffinic fuel + 5% palm biodiesel), BP8020 (80% paraffinic fuel + 20% palm biodiesel), and BP100 (100% paraffinic fuel; Table 1). Experimental results indicated that B100, BP9505, BP8020, and BP100 were much safer when stored than PDF. However, we must use additives so that B100 and BP100 will not gel as quickly in a cold zone. Using B100, BP9505, and BP8020 instead of PDF reduced PM, THC, and CO emissions dramatically but increased CO₂ slightly because of more complete combustion. The CO₂-increased fraction of BP9505 was the lowest among test blends. Furthermore, using B100, B20, BP9505, and BP8020 as alternative fuels reduced total PAHs and total benzo[a]pyrene equivalent concentration (total BaP_eq) emissions significantly. BP9505 had the lowest decreased fractions of power and torque and increased fraction of BSFC. These experimental results implied that BP9505 is feasible for traveling diesel vehicles. Moreover, paraffinic fuel will likely be a new alternative fuel in the future. Using BP9505 instead of PDF decreased PM (22.8%), THC (13.4%), CO (25.3%), total PAHs (88.9%), and total BaP_eq (88.1%) emissions significantly.     

Determination of source contributions to ambient PM2.5 in Kaohsiung, Taiwan, using a receptor model

Ambient particulates of PM2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM2.5. The mean concentration of ambient PM2.5 was 42.69-53.68 micrograms/m3 for the sampling period. The abundant species in ambient PM2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO4(2-) (12.8-15.1%), NO3- (8.1-10.3%), NH4+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO4(2-) and NO3-), and outdoor burning of agriculture wastes (13-17%).     

Source apportionment of fine particles in Washington, DC, utilizing temperature-resolved carbon fractions

Integrated ambient particulate matter < or =2.5 microm in aerodynamic diameter (PM2.5) samples were collected at a centrally located urban monitoring site in Washington, DC, on Wednesdays and Saturdays using Interagency Monitoring of Protected Visual Environments samplers. Particulate carbon was analyzed using the thermal optical reflectance method that divides carbon into four organic carbon fractions, pyrolyzed organic carbon, and three elemental carbon fractions. A total of 35 variables measured in 718 samples collected between August 1988 and December 1997 were analyzed. The data were analyzed using Positive Matrix Factorization and 10 sources were identified: sulfate (SO4(2-))-rich secondary aerosol I (43%), gasoline vehicle (21%), SO4(2-)-rich secondary aerosol II (11%), nitrate-rich secondary aerosol (9%), SO4(2-)-rich secondary aerosol III (6%), incinerator (4%), aged sea salt (2%), airborne soil (2%), diesel emissions (2%), and oil combustion (2%). In contrast to a previous study that included only total organic carbon and elemental carbon fractions, motor vehicles were separated into fractions identified as gasoline vehicle and diesel emissions containing carbon fractions whose abundances were different between the two sources. This study indicates that the temperature-resolved carbon fraction data can be utilized to enhance source apportionment, especially with respect to the separation of diesel emissions from gasoline vehicle sources. Conditional probability functions using surface wind data and deduced source contributions aid in the identifications of local sources.     

Antibiotic resistance of Enterococcus spp. isolated from wastewater and sludge of poultry slaughterhouses

Antibiotimicrobial resistance was investigated in 537 Enterococcus spp. isolates recovered from 22 samples of crude inflow, treated effluent and sludge collected in wastewater treatment plants of eight poultry slaughterhouses of Portugal. No significant differences (P > 0.05) were found in the resistance to each antimicrobial agent with regards to the origin of the sample (inflow, sludge and effluent). Many of the isolates displayed resistance to tetracycline (85.7%), erythromycin (45.7%), nitrofurantoin (34.0%) and rifampicin (17.8%). Resistance was also observed, but to a lesser extent, to ciprofloxacin (10.2%), ampicillin (8.0%), chloramphenicol (4.6%), vancomycin (0.9%) and gentamicin (0.4%). Resistance to three or more antimicrobial classes was present in 37.1% of the isolates. Wastewater treatment resulted in viable enterococci decrease between less than 1 log and 4 log; nevertheless, more than 4.4 x 10(5) colony forming units (CFU)/100 mL were present in the outflow of the plants and thus resistant enterococci are not prevented from reaching the general environment.     

Estimation of source apportionment and potential source locations of PM2.5 at a west coastal IMPROVE site

Particle composition data for PM_2.5 samples collected at Kalmiopsis Interagency Monitoring of Protected Visual Environments (IMPROVE) site in southwestern Oregon from March 2000 to May 2004 were analyzed to provide source identification and apportionment. A total of 493 samples were collected and 32 species were analyzed by particle induced X-ray emission, proton elastic scattering analysis, photon-induced X-ray fluorescence, ion chromatography, and thermal optical reflectance methods. Positive matrix factorization (PMF) was used to estimate the source profiles and their mass contributions. The PMF modeling identified nine sources. In the Kalmiopsis site, the average mass was apportioned to wood/field burning (38.4%), secondary sulfate (26.9%), airborne soil including Asian dust (8.6 %), secondary nitrate (7.6%), fresh sea salt (5.8%), OP-rich sulfate (4.9%), aged sea salt (4.5 %), gasoline vehicle (1.9%), and diesel emission (1.4%). The potential source contribution function (PSCF) was then used to help identify likely locations of the regional sources of pollution. The PSCF map for wood/field burning indicates there is a major potential source area in the Siskiyou County and eastern Oregon. The potential source locations for secondary sulfate are found in western Washington, northwestern Oregon, and the near shore Pacific Ocean where there are extensive shipping lanes. It was not possible to extract a profile directly attributable to ship emissions, but indications of their influence are seen in the secondary sulfate and aged sea salt compositions.