Sorptive behavior of nitro-PAHs in street runoff and their potential as indicators of diesel vehicle exhaust particles

This is the first report to reveal the particle-water distribution of nitropolycyclic aromatic hydrocarbons (NPAHs) and to discuss their potential risks and utility as indicators of diesel vehicle exhaust particles (DEP). Time-series samples of runoff were collected from a highway, and NPAHs and polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography-mass spectrometry (GC-MS) to study their dynamic behavior. The concentrations of total NPAHs ranged from 11 to 73 ng/L in particulate phase (>0.7 mcirom) and from 2.3 to 4.9 ng/L in dissolved phase (<0.7 microm). Like their PAH analogs, most (81-97%) NPAHs were associated with particulate matter. The organic carbon-normalized in situ partition coefficients (Koc') of NPAHs observed in runoff events (10(5.8-6.3) for 2-nitrofluoranthene and 10(5.8-6.2) for 1-nitropyrene [1-NP]) were more than 1 order of magnitude higher than those expected from their Kow, indicating great affinity for particulate matter such as soot. Concentrations of PAHs and NPAHs adjusted by potency equivalency factors and induction equivalency factors showed that the potential risks of NPAHs were smaller than those of PAHs by a factor of more than a hundred for the particulate phase and morethan fourforthe dissolved phase. Comparison of concentrations and compositions of NPAHs and PAHs among runoff, DEP, gasoline vehicle exhaust particles, boiler exhaust particles, and aerosols suggested that the ratio of 1-NP to total PAHs (1-NP/PAH) is a useful indicator of DEP for source apportionment of PAHs among traffic-related sources. Source-apportionment of PAHs in the runoff by 1-NP/PAH and methylphenanthrene/phenanthrene ratios suggested that most PAHs in the runoff except the second flush peak were derived from DEP but that other pyrogenic sources contributed to the particles at the second flush and thus to the overall runoff particles.     

Kinetic studies of heterogeneous reactions of polycyclic aromatic hydrocarbon aerosols with NO₃ radicals

Polycyclic aromatic hydrocarbons (PAHs) and their derivates are mutagenic and carcinogenic substances widely distributed in the atmospheric environment. In this study, effective rate constants for heterogeneous reactions of NO(3) radicals with five 4-ring PAHs [benzo[a]anthracene (BaA), chrysene (Ch), pyrene (Py), 1-nitropyrene (1-NP), and 1-hydroxypyrene (1-OHP)] adsorbed on suspended azelaic acid particles are investigated by a mixed-phase relative rate method with gas-phase isoprene as the reference substance. The concentrations of suspended PAH particles and gas-phase isoprene are monitored concurrently by a real-time vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and an online atmospheric gas analysis mass spectrometer, respectively. The obtained effective rate constants for the reactions of BaA, Ch, Py, 1-NP, and 1-OHP particles with NO(3) radicals are 4.3 × 10(-12), 4.0 × 10(-12), 6.4 × 10(-12), 1.3 × 10(-12), and 1.0 × 10(-11) cm(3)·molecule(-1)·s(-1), respectively, and their corresponding atmospheric lifetimes range from several minutes to half an hour at the NO(3) radical concentration of 5 × 10(8) molecules·cm(-3). In addition, the NO(3) uptake coefficients on particulate PAHs are estimated according to the consumption of PAHs under the exposure of NO(3) radicals. The experimental results of these heterogeneous reactions in the aerosol state provide supplementary knowledge for kinetic behaviors of airborne PAHs particles.     

Lignin-derived phenols in Houston aerosols: implications for natural background sources

Solvent-extractable monomeric methoxyphenols in aerosol samples conventionally have been used to indicate the influence of biomass combustion. In addition, the presence of lignin oxidation products (LOP), derived from the CuO oxidation of vascular plant organic matter, can help trace the source and inputs of primary biological particles in aerosols. Ambient aerosols (coarse and fine) collected in Houston during summer 2010 were analyzed by gas chromatography-mass spectrometry to characterize monomeric and polymeric sources of LOPs. This is the first time polymeric forms of the LOPs have been characterized in ambient aerosols. The absence or small concentrations of solvent-extractable monomeric LOPs and levoglucosan isomers point to the limited influence of biomass burning during the sampling period. The trace levels of anhydrosugar concentrations most likely result from long-range transport. This observation is supported by the absence of co-occurring lignin monomers that undergo photochemical degradation during transport. The larger concentration (142 ng m(-3)) of lignin polymers in coarse aerosols shows the relative importance of primary biological aerosol particles, even in the urban atmosphere. The LOP parameters suggest a predominant influence from woody tissue of angiosperms, with minor influence from soft tissues, gymnosperms, and soil organic matter.     

Absorption and adsorption of hydrophobic organic contaminants to diesel and hexane soot

Soot particles vary in pore structure, surface properties, and content of authigenic (native) extractable organic chemicals. To better understand the effects of these properties on sorption, aqueous sorption isotherms for 14C-labeled phenanthrene and 1,2,4-trichlorobenzene were obtained for four soots of varying properties: two diesel reference soots, a hexane soot, and an ozonated hexane soot. Substantial isotherm nonlinearity was observed. In comparison to diesel soot SRM 2975, diesel soot SRM 1650b had a much higher content of extractable authigenic organic chemicals, showed less sorption of 14C-labeled sorbate at low relative concentrations (Ce/Sw), and showed higher sorption at high Ce/Sw. In comparison to normal hexane soot, the ozonated hexane soot had a higher surface O/C ratio and showed substantially less sorption at all concentrations studied. The sorption differences were attributed to the noted differences in properties, and results were interpreted through a dual-mode sorption model that included the possibility of both surface adsorption (modeled using a Polanyi-based approach) and simple phase partitioning (linear absorption). Generally, such modeling indicated that overall uptake at low concentrations in all four soots was dominated by surface adsorption but that sorption at higher sorbate concentrations in SRM 1650b was heavily influenced by linear absorption within the natively bound organic phase.     

Identification and determination of highly carcinogenic dibenzopyrene isomers in air particulate samples from a street canyon, a rooftop, and a subway station in Stockholm

This study presents determined levels of the highly carcinogenic dibenzopyrene isomers dibenzo(a,l)pyrene, dibenzo(a,e)pyrene, dibenzo(a,l)pyrene, and dibenzo(a,h)pyrene as well as three other polycyclic aromatic hydrocarbons (PAHs)--benzo(a)pyrene, perylene and coronene--in ambient particulate material samples from a street canyon, a rooftop, and an underground subway station in Stockholm, Sweden. To our knowledge, these are the first reported determinations of dibenzopyrene isomers in air particles from either Stockholm or a subway station. Taking into account both concentration and toxic equivalence factors (TEFs), the PAH with the highest carcinogenic potency in the analyzed samples was dibenzo(a,l)pyrene, and the sum carcinogenic potency of the determined dibenzopyrenes was about 1-4 times higher than that of benzo(a)pyrene in the analyzed samples. These findings indicate that it is important to analyze the dibenzopyrene isomers as well as benzo(a)pyrene; the common approach of using benzo(a)pyrene as an indicator substance could lead to underestimates of the potential carcinogenic potency of PAHs in ambient air. The results also indicate that the relative carcinogenic potency of the determined dibenzopyrenes and benzo(a)pyrene in air particles from Stockholm is similar to that of air particles sampled in Washington in 1976-1977, despite general improvements in air quality in the intervening period. However, more data are needed to characterize temporal variations in dibenzopyrene levels in locations such as subway stations, suburbs, road tunnels, and metropolitan areas. There is also a need to identify and characterize both stationary and mobile PAH sources with respect to emission of dibenzopyrene isomers.     

Diurnal variations of individual organic compound constituents of ultrafine and accumulation mode particulate matter in the Los Angeles Basin

Individual organic compounds can be used as tracers for primary sources of ambient particulate matter (PM) in chemical mass balance receptor models. Previous work has examined PM2.5 only and usually over long sampling periods encompassing entire days or longer. In this study, a high-flow-rate, low-pressure-drop ultrafine particle separator was deployed to collect sufficient mass for organic speciation of ultrafine and accumulation mode aerosol on a diurnal basis. Particles between 0.18 and 2.5 microm in diameter were collected on a quartz-fiber impaction substrate, and ultrafine particles below 0.18 microm were collected downstream on a high-volume filter. Four daily time period samples (morning, midday, evening, and overnight) were sampled over five weekdays to form a weekly average composite for each diurnal period. Sampling was conducted at two sites over two seasons; summer (August) and winter (January) samples were collected at both an urban site near downtown Los Angeles (University of Southern California) and a downwind, inland site in Riverside, CA. Hopanes, used as organic markers for vehicular emissions, were found to exist primarily in the ultrafine mode. Levoglucosan, an indicator of wood combustion, was quantified in both size ranges, but more was present in the accumulation mode particles. An indicator of photochemical secondary organic aerosol formation, 1,2-benzenedicarboxylic acid, was found primarily in the accumulation mode and varied with site, season, and time of day as one would expect for a photochemical product. The atmospheric variations of particulate cholesterol and other organic acids were also considered. By examining the diurnal variation, size-fractionation, and intercorrelations of individual organic compounds, the sources and atmospheric fate of these tracers can be better understood and their utility as molecular markers can be assessed.     

Mobile laboratory with rapid response instruments for real-time measurements of urban and regional trace gas and particulate distributions and emission source characteristics

Recent technological advances have allowed the development of robust, relatively compact, low power, rapid response (approximately 1 s) instruments with sufficient sensitivity and specificity to quantify many trace gases and aerosol particle components in the ambient atmosphere. Suites of such instruments can be deployed on mobile platforms to study atmospheric processes, map concentration distributions of atmospheric pollutants, and determine the composition and intensities of emission sources. A mobile laboratory containing innovative tunable infrared laser differential absorption spectroscopy (TILDAS) instruments to measure selected trace gas concentrations at sub parts-per-billion levels and an aerosol mass spectrometer (AMS) to measure size resolved distributions of the nonrefractory chemical components of fine airborne particles as well as selected commercial fast response instruments and position/velocity sensors is described. Examples of the range of measurement strategies that can be undertaken using this mobile laboratory are discussed, and samples of measurement data are presented.     

Isomer-specific degradation of branched and linear 4-nonylphenol isomers in an oxic soil

Using (14)C- and (13)C-ring-labeling, degradation of five p-nonylphenol (4-NP) isomers including four branched (4-NP(38), 4-NP(65), 4-NP(111), and 4-NP(112)) and one linear (4-NP(1)) isomers in a rice paddy soil was studied under oxic conditions. Degradation followed an availability-adjusted first-order kinetics with the decreasing order of half-life 4-NP(111) (10.3 days) > 4-NP(112) (8.4 days) > 4-NP(65) (5.8 days) > 4-NP(38) (2.1 days) > 4-NP(1) (1.4 days), which is in agreement with the order of their reported estrogenicities. One metabolite of 4-NP(111) with less polarity than the parent compound occurred rapidly and remained stable in the soil. At the end of incubation (58 days), bound residues of 4-NP(111) amounted to 54% of the initially applied radioactivity and resided almost exclusively in the humin fraction of soil organic matter, in which chemically humin-bound residues increased over incubation. Our results indicate an increase of specific estrogenicity of the remaining 4-NPs in soil as a result of the isomer-specific degradation and therefore underline the importance of understanding the individual fate (including degradation, metabolism, and bound-residue formation) of isomers for risk assessment of 4-NPs in soil. 4-NP(1) should not be used as a representative of 4-NPs for studies on their environmental behavior.     

Predicted intake of trace elements and minerals via household drinking water by 6-year-old children from Kraków (Poland). Part 1: lead (year 2000).

A population of 232 children living in urban, peripheral and rural areas of southern Poland was included in the study. Household drinking water was collected twice a day, early in the morning and in the evening. The lead (Pb) concentration was estimated by a graphite furnace-atomic absorption spectroscopy (GF-AAS) method. The geometric mean of Pb concentration in drinking water in 2000 for evening samples was 0.68, 1.24 and 2.28 microg x l(-1) for urban, peripheral and rural areas, respectively, while for morning samples it was 1.42, 2.16 and 2.97 microg x l(-1). These areas differed significantly (p < 0.05) and odds ratio for peripheral versus urban areas was 1.6. The difference of Pb concentrations in the morning and evening water was significant (p < 0.001). The mean ratio was 1.8 and the median difference 0.8 microg x l(-1). The predicted contribution of drinking water to the Pb intake by 6-year-old children living in urban, peripheral and rural areas was 1.2, 2.0 and 5.6% of the provisional tolerable weekly intake (PTWI) respectively. For the 4.3-11.1% of children, the Pb concentration in water > 10 microg x l(-1) and in these cases the predicted Pb intake with drinking water contributed to PTWI by 22.3-30.0%. The simple test introduced in this study, the analysis of morning and evening water samples, proved that contamination of water in the plumbing is significant and common. The above parameters can be applied to routine quality control of drinking water performed in the households. The in-house water contamination should be considered as a factor in public health protection programmes with special attention to children.     

Origin, occurrence, and source emission rate of acrolein in residential indoor air

Acrolein, a volatile, unsaturated aldehyde, is a known respiratory toxicant and one of the 188 most hazardous air pollutants identified by the U.S. EPA. A newly developed analytical method was used to determine residential indoor air concentrations of acrolein and other volatile aldehydes in nine homes located in three California counties (Los Angeles, Placer, Yolo). Average indoor air concentrations of acrolein were an order of magnitude higher than outdoor concentrations at the same time. All homes showed similar diurnal patterns in indoor air concentrations, with acrolein levels in evening samples up to 2.5 times higherthan morning samples. These increases were strongly correlated with temperature and cooking events, and homes with frequent, regular cooking activity had the highest baseline (morning) acrolein levels. High acrolein concentrations were also found in newly built, uninhabited homes and in emissions from lumber commonly used in home construction, suggesting indoor contributions from off-gassing and/or secondary formation. The results provide strong evidence that human exposure to acrolein is dominated by indoor air with little contribution from ambient outdoor air.     

Predicted intake of trace elements and minerals via household drinking water by 6-year-old children from Krakow (Poland). Part 4: Copper

The aim of this study was to assess exposure of children to copper (Cu) from household drinking water (DW). DW samples were collected between 1997 and 2004 in ～650 households and pre-schools using a double-sampling method (morning – W1; evening – W2). The study group comprised ～300 children (5–7 years old) living in Krakow (urban, peripheral) and rural areas in southern Poland. Cu concentrations were determined by flame atomic absorption spectrometry. There was no significant relationship between the sampling period and Cu concentration, but statistically significant differences were found between urban and non-urban (rural, peripheral) sites and between morning and evening samples. Geometric means of Cu concentration in evening DW (95% confidence interval, in μg L^?1) were 8 (1–110), 20 (1–274) and 12 (0–364) in urban, peripheral and rural sites, respectively. DW contamination after overnight standing was comparable in all sites (average increase ～20 μg Cu L^?1). The adopted threshold of 100 μg Cu L^?1 was exceeded in evening DW by 3.6 and 15% in urban and non-urban households, respectively. Exceedance of the EC limit (2 mg L^?1) was not significant. The mean predicted contribution of evening DW to Cu intake by children were 18–37 μg day^?1 or 0.8–1.6 μg kg^?1 bw day^?1 but were 2–3-fold higher for morning DW. The Polish RDA (1 mg Cu day^?1) was exceeded for morning (evening) DW in 3.7 (0.2)% of children, with a mean intake of 159 (118)% of RDA. The observed copper levels and predicted intakes can be considered low and should not raise nutritional or toxicological concerns for the age group studied. Nevertheless, due to overnight contamination, the suggestion that the stagnant portion of drinking water should be discarded remains valid.     

Atmospheric chlorine chemistry in southeast Texas: impacts on ozone formation and control

Recent evidence has demonstrated that chlorine radical chemistry can enhance tropospheric hydrocarbon oxidation and has the potential to enhance ozone formation in urban atmospheres. To assess these effects quantitatively, an August-September 2000 photochemical episode in southeast Texas was simulated using the comprehensive air quality model, with extensions (CAMx). During this episode, ambient measurements of a unique marker of atmospheric chlorine chemistry, 1-chloro-3-methyl-3butene-2-one (CMBO), were made and model performance was assessed by comparing modeled and observed CMBO mixing ratios. The model predicted ambient CMBO mixing ratios within the uncertainty limits associated with the emissions inventory, so the model was used to assess the impacts of chlorine chemistry on ozone formation. Based on the current emissions inventory, chlorine emissions have the potential to enhance 1-h-averaged ozone mixing ratios by 70 ppb, in very localized areas, during morning hours. Over wider areas, and at times of day when peak ozone concentrations are observed, the impacts of chlorine emissions on ozone concentrations are typically less than 10 ppb. Chlorine emissions also influenced changes in ozone concentrations due to hydrocarbon and NOx emission controls.     

Concentration and distribution of platinum group elements (Pt, Pd, Rh) in airborne particulate matter in Frankfurt am Main, Germany

The concentrations and distribution of platinum group elements (Pt, Pd, Rh) in airborne particulate matter were studied in a period of one year from August 2001 to July 2002 in urban and in nonurban areas. Airborne dust samples were collected as a total amount (particles with an aerodynamic diameter <22 microm) and classified using an eight-stage Andersen impactor (<10 microm) at three locations with different traffic density roads in the Frankfurt am Main and nonurban areas. Sampling at the three locations was performed simultaneously for total airborne dust and fractionated airborne dust. Pd was determined by total reflection X-ray fluorescence after Hg coprecipitation. Pt and Rh were analyzed by adsorptive striping voltammetry after HPA digestion. The results show that the PGE concentrations in airborne samples depend on the traffic density. The highest PGE concentrations in air were found in the vicinity of major roads with heavy traffic, and the lowest ones were found in the nonurban area. The presence of PGE at the sampling station relatively free of traffic in a nonurban area hints to a transport of some of the emitted PGE from the city to this station by wind. At all three sampling locations, a heterogeneous distribution of the Pd, Pt, and Rh concentrations during the sampling year can be observed. The sum of PGE concentrations in total airborne dust is comparable with the sum of impactor samples. However, the concentration of Pt and Rh in total airborne dust (<22 microm) is on average higher than in impactor samples (<10 microm). On the contrary, Pd concentration is higher in impactor samples in most cases. The airborne PGE distribution is dominated by Pt, followed by Pd and Rh. The impactor samples are dominated by Pd, followed by Pt and Rh. This fact indicates that palladium occurs mainly in relatively fine airborne particles. The main fraction of PGE is found on average in particle sizes between 1.1 and 4.7 microm. Knowledge of the size distribution of particles containing PGE is important with respect to risk assessment of human inhalation.     

Association of plasma insulin concentration to fatty acid distribution between milk fat and membrane synthesis

We examined the association between plasma insulin concentration and fatty acid distribution to milk fat and membrane fractions (triglyceride and phospholipid, respectively) in dairy cows. Thirty-seven Holstein cows at 60 to 70 d postpartum were synchronized by 2 PGF(2α) injections 14 d apart. Plasma samples were taken before morning and evening milkings and milk samples were obtained at morning milking. Plasma insulin concentrations were determined and cows were retrospectively assigned to low insulin (LI; 2.8±0.2 ng/mL, n=6) or high insulin (HI; 5.9±0.6 ng/mL, n=7) experimental groups. Fatty acid analysis of milk samples demonstrated a possible association between plasma insulin concentration and the fatty acid composition in phospholipid and triglyceride fractions. In the HI group, monounsaturated fatty acid concentration tended to be higher in the triglyceride (Tg) fraction than the phospholipids (Pl) fraction. In the LI group, the concentrations of short- and medium-chain saturated fatty acids (<16 carbon chain length), considered de novo-synthesized fatty acids, were higher in the triglyceride fraction than the phospholipid fraction. These results imply that the primary source of saturated fatty acids for phospholipid synthesis, in both HI and LI groups, is the circulation, as reflected by a higher concentration of longer saturated fatty acids (>16 carbon chain length) in the phospholipid fraction. Finally, the phospholipid-to-triglyceride ratio was higher in the HI group than in the LI group. Together, the results indicate that fatty acid distribution between phospholipid (membrane) and triglyceride (fat) synthesis by the mammary gland is associated with fatty acid length, degree of unsaturation, and origin, and might be subject to metabolic hormone regulation. Furthermore, a lower triglyceride-to-phospholipid ratio in the HI group implies that high plasma insulin and low milk fat concentrations are associated with a shift in the size distribution of milk fat globules.     

Diurnal fluctuations in polybrominated diphenyl ether concentrations during and after a severe dust storm episode in Kuwait City, Kuwait

Concentrations of polybrominated diphenyl ethers (PBDEs) were quantified in four-hour integrated air samples obtained serially over a five day period in May 2007 in Kuwait City during and after a severe dust storm. The ∑PBDE concentrations ranged from 51 to 1307 pg m(-3) for the first two days of sampling and 20 to 148 pg m(-3) for the rest of the sampling period. The first two days of sampling occurred during a severe dust storm episode when the total suspended particulates (TSP) in air exceeded 1000 μg/m(3) with concentrations peaking during the day and decreasing at night. During this dust episode, the peak nighttime PBDE concentration was 30 times higher than the minimum daytime concentration. Although ∑PBDE concentrations peaked at night during the first two sampling days, the fluctuations in the BDE 47:99 ratio tracked changes in ambient temperature remarkably well, following a clear diurnal pattern. The fraction of congeners in the gas phase varied inversely with solar flux and was lower on days with a high number of hours of sunshine, suggesting that photolytic degradation of gas-phase PBDEs was occurring.     

Identification of particulate matter sources on an hourly time-scale in a wood burning community

Particulate matter (PM) sources at two different sites in a rural town in New Zealand were investigated on an hourly time-scale. Streaker samplers were used to collect hourly, size-segregated PM(10-2.5) and PM(2.5) samples that were analyzed for elemental content using ion beam analysis techniques. Black carbon concentrations were determined using light reflection and PM(10) concentrations were recorded using colocated continuous PM monitors. PM(10) concentrations at both sites displayed a diurnal pattern, with hourly PM(10) concentration maxima in the evening (7 pm-midnight) and in the morning (7-9 am). One of the monitoring sites experienced consistently higher average PM(10) concentrations during every hour and analysis indicated that katabatic flows across the urban area contributed to the increased concentrations observed. Source apportionment using positive matrix factorization on the hourly data revealed four primary PM(10) sources for each site: biomass burning, motor vehicles, marine aerosol and crustal matter. Biomass burning was the most dominant source at both sites and was responsible for both the evening and morning PM(10) concentration peaks. The use of elemental speciation combined with PM(10) concentrations for source apportionment on an hourly time-scale has never been reported and provides unique and useful information on PM sources for air quality management.     

Cow and environmental factors associated with protein fractions and free amino acids predicted using mid-infrared spectroscopy in bovine milk

The objective of the present study was to identify the factors associated with both the protein composition and free amino acid (FAA) composition of bovine milk predicted using mid-infrared spectroscopy. Milk samples were available from 7 research herds and 69 commercial herds. The spectral data from the research herds comprised 94,286 separate morning and evening milk samples; the spectral data from the commercial herds comprised 40,260 milk samples representing a composite sample of both the morning and evening milkings. Mid-infrared spectroscopy prediction models developed in a previous study were applied to all spectra. Factors associated with the predicted protein and FAA composition were quantified using linear mixed models. Factors considered in the model included the fixed effects of calendar month of the test, milking time (i.e., morning, evening, or both combined), parity (1, 2, 3, 4, 5, and ≥6), stage of lactation, the interaction between parity and stage of lactation, breed proportion of the cow (Friesian, Jersey, Norwegian Red, Montbéliarde, and other), and both the general heterosis and recombination coefficients of the cow. Contemporary group as well as both within- and across-lactation permanent environmental effects were included in all models as random effects. Total proteins (i.e., total casein, CN; total whey; and total β-lactoglobulin) and protein fractions (with the exception of α-lactalbumin) decreased postcalving until 36 to 65 days in milk and increased thereafter. After adjusting the statistical model for differences in crude protein content and milk yield separately, irrespective of stage of lactation, younger animals produced more total proteins (i.e., total CN, total whey, and total β-lactoglobulin) as well as more total FAA, Glu, and Asp than their older contemporaries. The concentration of all protein fractions (except β-CN) in milk was greatest in the evening milk, even after adjusting for differences in the crude protein content of the milk. Relative to a purebred Holstein cow, Jersey cows, on average, produced a greater concentration of all CN fractions but less total FAA, Glu, Gly, Asp, and Val in milk. Relative to their respective purebred parental average, first-cross cows produced more total CN and more β-CN. Results from the present study indicate that many cow-level factors, as well as other factors, are associated with protein composition and FAA composition of bovine milk.     

Daily variation in chemical characteristics of urban ultrafine aerosols and inference of their sources

A summer air quality monitoring campaign focusing on daily variation of ultrafine (<180 nm in diameter) particle chemical characteristics was conducted in a typical urban site in Los Angeles during June-July 2006. Ultrafine particles (UFP) were collected weekly for two 3 h periods each day, one to capture the morning commute (06:00-09:00 PDT) (Pacific Daylight Time) and one to investigate photochemically altered particles (13:00-16:00 PDT). Samples were analyzed for ionic compounds, metals, trace elements, elemental carbon, and organic carbon. In addition, measurements of individual organic species and their variation with time of day at the urban site were conducted. The relative abundances of alkanes, PAH, and hopanes in the morning denote a strong influence of commute traffic emissions on ultrafine particle concentrations. By contrast, afternoon concentrations of oxygenated organic acids and sulfate rose, while other species were diluted by increased mixing height or lost due to increasing temperature. These are clear indicators that secondary photochemical reactions are a major formation mechanism of ultrafine aerosols in the afternoon. The concentrations of organic species originating from vehicular emissions measured in this study compare favorably to those from freeway-adjacent measurements by using CO2 concentrations to adjust for dilution, demonstrating the effectiveness of this tool for relating sites affected by vehicular emissions.     

Short communication: Effect of grazing on the concentrations of total sialic acid and hexose in bovine milk

Sialic acid, which is located at the terminal end of glycoconjugates, is believed to have important biological functions. Its concentration in bovine milk varies depending on lactation stage and season. However, it remains unclear whether dietary factors, especially fresh forage, affect the total sialic acid concentration in milk. The purpose of the present study was to investigate the effect of grazing on the concentrations of total sialic acid and hexose in bovine milk. Six healthy dairy cows were used in a crossover design (3 cows fed fresh forage and 3 cows fed grass silage) for 2 wk. Individual milk samples were collected at 2 consecutive milkings (morning and evening) at 0, 1, 3, 5, 8, 11, and 14 d of the experimental period, and 2 consecutive samples in each cow were combined on each sampling day in proportion of the morning and evening milk yields. No differences in body weight, milk yield, or milk composition were observed between the 2 groups during the experimental period. The hexose concentration in milk did not differ between these groups during the experimental period. Conversely, the total sialic acid concentration in the milk of each grazing cow significantly increased at 11 and 14 d of the experimental period compared with that at 0 d. In the grass silage group, the total sialic acid concentration at the end of the experimental period tended to be lower than that at 0 d, but the decrease was not significant. These results indicate that grazing management could have increased the concentration of sialoglycoconjugates in milk. This suggests that grazing may increase the biological function of milk because it is thought that sialic acid is significant in many ways.