Size and composition distributions of particulate matter emissions: part 1--light-duty gasoline vehicles

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965-2003; odometer readings 1264-207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-microm aerodynamic diameter) and fine PM1.8 (< or =1.8-microm aerodynamic diameter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emissions of 51 microg/km and 371 microg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1- and 0.18-microm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 microm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Fugitive emissions opacity determination using the digital opacity compliance system (DOCS)

Maintenance of Department of Defense (DoD) weapon systems, conducting battlefield training exercises as well as meeting military construction and/or demolition schedules, invariably generate fugitive air emissions, many of which are visible. Although there is no codified federal method for quantifying fugitive emissions opacity, many state and local air regulatory agencies have instituted enforceable fugitive emission opacity standards at DoD facilities. The current study focused on comparing the performance of the digital opacity compliance system (DOCS) with U.S. Environment Protection Agency Method 9 (Method 9) certified human observers in quantifying the visible opacity associated with fugitive emissions produced using a commercial fog generator. By systematically repositioning both DOCS cameras and Method 9-certified observers during field testing, differences in method performance as a function of observational locations were documented. At both the 30- and 300-ft off-set distances, opacity levels reported by the DOCS technology and Method 9-certified smoke readers were found to be statistically different at the 99% confidence level. Alternatively, at the 90- and 150-ft off-set distances, results suggested that there was an insignificant difference at the 99% confidence level between the two methods. Comparing the magnitude of the each method's standard deviation suggested that, at the 30-ft off-set distance, the DOCS technology was consistently more precise than Method 9-certified readers regardless of the observer's downwind distance. However, at the 90, 150, and 300-ft off-set distances, method precision seemed to vary as a function of both off-set and downwind distance. The primary factor affecting the consistency in opacity measurements appeared to be the impact of ground-level air turbulence on fog plume dispersion and transport. Field observations demonstrated that localized wind shear played a critical and decisive role in how and to what extent fugitive emissions opacity could be determined, regardless of the method selected.     

International trade in meat: the tip of the pork chop

This paper provides an original account of global land, water, and nitrogen use in support of industrialized livestock production and trade, with emphasis on two of the fastest-growing sectors, pork and poultry. Our analysis focuses on trade in feed and animal products, using a new model that calculates the amount of "virtual" nitrogen, water, and land used in production but not embedded in the product. We show how key meat-importing countries, such as Japan, benefit from "virtual" trade in land, water, and nitrogen, and how key meat-exporting countries, such as Brazil, provide these resources without accounting for their true environmental cost. Results show that Japan's pig and chicken meat imports embody the virtual equivalent of 50% of Japan's total arable land, and half of Japan's virtual nitrogen total is lost in the US. Trade links with China are responsible for 15% of the virtual nitrogen left behind in Brazil due to feed and meat exports, and 20% of Brazil's area is used to grow soybean exports. The complexity of trade in meat, feed, water, and nitrogen is illustrated by the dual roles of the US and The Netherlands as both importers and exporters of meat. Mitigation of environmental damage from industrialized livestock production and trade depends on a combination of direct-pricing strategies, regulatory approaches, and use of best management practices. Our analysis indicates that increased water- and nitrogen-use efficiency and land conservation resulting from these measures could significantly reduce resource costs.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

Variations in PCB concentrations between genders of six warmwater fish species in Lake Logan Martin, Alabama, USA

We collected and analyzed 955 individual fish (six species) for sexual differences in PCB bioaccumulations from a southeastern, USA reservoir. Using 2-way ANCOVAs, we found significant differences in fillet PCB concentrations between sexes for channel catfish (Ictalurus punctatus), largemouth bass (Micropterus salmoides) and spotted bass (Micropterus punctulatus). Striped bass (Morone saxatilus), black crappie (Pomoxis nigromaculatus) and freshwater drum (Aplodinotus grunniens) did not display differences between sexes in PCB concentrations. We suspect that sexual differences may be due to biological differences in reproduction, relative motility and lipid deposition. For one species (striped bass), sexual differences in PCB concentrations were inconsistent with a study in the Hudson River suggesting that sexual differences in bioaccumulations can change across ecosystems. Two species which did show sexual differences, largemouth bass and channel catfish, are often chosen as representative species (e.g., "piscivore" and "benthivore") in contaminant monitoring in many USA states indicating human consumption and risk management decisions would be improved if an equal number of male and female fish were included in composite PCBs analysis. This could reduce variability in fish PCBs data from which consumption advisories are based.     

Effect of coumaphos on cholinesterase activity, hematology, and biochemical blood parameters of bovines in tropical regions of Mexico

To assess the effect of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] exposure on physiological responses during bovine production, acetylcolinesterase (AChE) and butyrylcholinesterase (BuChE) activities were measured in whole blood, erythrocytes, and plasma of healthy male steers (Bos Taurus x Bos indicus) sprayed with coumaphos at a non-lethal dose of 1 mg kg(- 1) body weight per day once every 14 (in vivo group) or 21 days (southern and central groups). Coumaphos topically administered at 1 mg/kg body weight per day to cattle under normal management practices in tropical areas produced a significant inhibition in erythrocyte (RBC) AChE and BuAChE activities when compared to baseline levels. RBC-AChE activity for the in vivo group decreased 71.3% (P < 0.05) and BuChE activity 59.1% (P < 0.05); RBC-AChE activity decreased 55.1% (P < 0.05) (southern group) and 43.4% (P < 0.05) (central group). Compared to the control specimens, steers from in vivo, southern, and central groups after 150 days of exposure had lower (P < 0.05) leukocyte count, absolute lymphocyte, erythrocyte, and platelet counts. Decreases in RBC-AChE activities correlated with decreased lymphocyte (r = 1.000, p = 0.01), erythrocyte (r = 1.000, p = 0.003), and platelet counts (r = 0.841, p = 0.036). Significantly increased BUN levels (P < 0.05) correlated with the decrease in RBC-AChE activities (r = - 0.997, p = 0.047) and with the decrease in absolute red blood cell (r = - 0.883, p = 0.020) and lymphocyte (r = - 0.825, p = 0.043) counts; increased (P < 0.05) total plasma protein levels correlated with the decrease in RBC-AChE activities (r = -0.998, p = 0.043), absolute red blood cell (r = - 0.998, p = 0.040), lymphocyte (r = - 0.893, p = 0.017), and platelet (r = -0.855, p = 0.030) counts. The physiological responses correlated with the erythrocyte acetylcholinesterase inhibition could be considered as early indicators or warning responses of bovine exposures to organophosphorus pesticides (OPs).     

Contaminant exposure in terrestrial vertebrates

Here we review mechanisms and factors influencing contaminant exposure among terrestrial vertebrate wildlife. There exists a complex mixture of biotic and abiotic factors that dictate potential for contaminant exposure among terrestrial and semi-terrestrial vertebrates. Chemical fate and transport in the environment determine contaminant bioaccessibility. Species-specific natural history characteristics and behavioral traits then play significant roles in the likelihood that exposure pathways, from source to receptor, are complete. Detailed knowledge of natural history traits of receptors considered in conjunction with the knowledge of contaminant behavior and distribution on a site are critical when assessing and quantifying exposure. We review limitations in our understanding of elements of exposure and the unique aspects of exposure associated with terrestrial and semi-terrestrial taxa. We provide insight on taxa-specific traits that contribute, or limit exposure to, transport phenomenon that influence exposure throughout terrestrial systems, novel contaminants, bioavailability, exposure data analysis, and uncertainty associated with exposure in wildlife risk assessments. Lastly, we identify areas related to exposure among terrestrial and semi-terrestrial organisms that warrant additional research.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Distribution of PAHs in Surface Soils from Petroleum Handling Facilities in Calabar

The level of concentrations of polycyclic aromatic hydrocarbons (PAHs) in surface soils from petroleum handling facilities (kerosene tank, generating plant, petrol stations, mechanic workshops, leaking pipeline and air port fuel dump) from Calabar metropolis southeastern Nigeria was determined by gas chromatography/ mass spectrometry. The results show that total polycyclic aromatic hydrocarbons (PAHs) varied from 1.80 to 334.43 mg/kg with a mean of 50.31 mg/kg. The lowest value of 1.80 mg/kg was obtained from petrol station while the highest value of 334.43 mg/kg was obtained from facility characterised by petrol stations and mechanic workshops. The ratio of phenanthrene/anthracene and fluoranthene/pyrene, varied from 0.43 to 27.72 and from 0.14 to 17.76 respectively. These ratios indicate various sources for the PAH. The two to three ring PAHs are the most abundant. Based on the PAH ratios and content alone it is not possible to distinguish between contribution from motor vehicle exhaust, gasoline spillage, used engine oil or petroleum production. However, considering the area of the study, it is very likely that the major source of soil contamination is originating from petroleum product.     

Removal of dinitrotoluenes from water via reduction with iron and peroxidase-catalyzed oxidative polymerization: a comparison between Arthromyces ramosus peroxidase and soybean peroxidase

A two-step process for the removal of dinitrotoluene from water is presented: zero-valent iron reduction is coupled with peroxidase-catalyzed polymerization of the resulting diaminotoluenes (DAT). The effect of pH was examined in the reduction step: at pH 6 the reaction occurred much more rapidly than at pH 8. In the second step, optimal pH and substrate ratio, minimal enzyme concentration and effect of polyethylene glycol (PEG) as an additive for greater than 95% conversion of DAT, over a 3h reaction period were determined using high performance liquid chromatography. Two enzymes were investigated and compared: Arthromyces ramosus peroxidase (ARP) and soybean peroxidase (SBP). The optimal pH values were 5.4 and 5.2 for ARP and SBP, respectively, but SBP was more resistant to mild acid whereas ARP was more stable in neutral solutions. SBP was found to have a greater hydrogen peroxide demand (optimal peroxide/DAT molar ratio for SBP: 2.0 and 3.0 for 2,4-diaminotoluene (2,4-DAT) and 2,6-diaminotoluene (2,6-DAT), respectively; for ARP: 1.5 and 2.75 for 2,4-DAT and 2,6-DAT, respectively) but required significantly less enzyme (0.01 and 0.1 U ml(-1) for 2,4-DAT and 2,6-DAT, respectively) to convert the DAT than ARP (0.4 and 1.5 U ml(-1) for 2,4-DAT and 2,6-DAT, respectively). PEG was shown to have no effect upon the degree of substrate conversion for either enzyme.