Study of nitro-polycyclic aromatic hydrocarbons in particulate matter in Dongguan

Total suspended and size-segregated atmospheric particles were collected in four seasons at three representative points in different functional areas of Dongguan City. The detailed size distributions of six nitro-PAHs [2-nitrofluorene (2-NF), 9-nitroanthracene, 2-nitrofluoranthene (2-NFL), 3-nitrofluoranthene, 1-nitropyrene, and 2-nitropyrene (2-NP)] were determined by high-performance liquid chromatography (HPLC) with UV detection using a binary elution gradient (methanol and water). We used a toxicity assessment based on potency equivalency factors (PEFs) to estimate the inhalation risk of the particulate matter. The results showed that, aside from 2-NF and 2-NFL, the content of the other four nitro-PAHs in the microparticles (<0.4 μm) were more than 20 %, a percentage significantly higher than other fractions of particulate matter. The seasonal distribution of nitro-PAHs shows that their concentrations were higher in the winter, while the PAH concentrations were higher in the summer. The study found that secondary formation (2-NFL and 2-NP) had a positive correlation with NO _x and NO₂, but a negative correlation with O₃. The benzo[a]pyrene equivalent (BaPeq) toxicity of particulate matter in Dongguan City ranged from 0.04 to 2.63 ng m^?3, and the carcinogenic index ranged from 0.04?×?10^?6 to 2.39?×?10^?6. These values do not represent a serious threat to human health.     

Occurrence and sources of particulate nitro-polycyclic aromatic hydrocarbons in ambient air in Denmark

The occurrence of selected nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) associated with atmospheric particulate matter has been investigated at an urban site and at a semi-rural site. For this purpose an analysis method based on gas chromatography and tandem ion trap mass spectrometry has been developed and applied. The nitro-PAH levels have been compared with levels of other air pollutants including unsubstituted PAHs, inorganic gases and particulate matter, as well as with meteorological parameters. Correlations and concentration ratios suggest that the dominant source of 9-nitroanthracene at the urban site is direct emissions, whereas at the semirural site its dominant source is atmospheric formation. The atmospheric formation of 2-nitrofluoranthene and 2-nitropyrene generally seems to be initiated by OH radicals during the day rather than by NO₃ radicals at night. The average contribution of the OH initiated formation is estimated to be in the range of 90–100%. However, under wintertime conditions with cloudy weather implying low OH radical production, NO₃ radicals may also be important as initiators of nitro-PAH formation. Samples influenced by transport of polluted air masses from the European continent have significantly elevated concentrations of atmospherically formed nitro-PAHs. The directly emitted nitro-PAHs, 1-nitropyrene and 3-nitrofluoranthene, do not exhibit elevated levels during such long-range transport episodes.     

Isomer distribution of nitrotriphenylenes in airborne particles, diesel exhaust particles, and the products of gas-phase radical-initiated nitration of triphenylene

The formation of mutagenic nitro-polycyclic aromatic hydrocarbons (NPAHs) 1- and 2-nitrotriphenylene (1- and 2-NTP) via gas-phase OH or NO₃ radical-initiated reactions of triphenylene was demonstrated for the first time using a flow reaction system. In contrast with the results of conventional electrophilic nitration, 2-NTP was formed in larger yield than 1-NTP, but this is consistent with the mechanism proposed for gas-phase radical-initiated nitration of PAH. In diesel exhaust particle (DEP) samples, both 1- and 2-NTP were identified and their concentrations determined, as well as 1-nitropyrene (1-NP), which is a representative combustion-derived NPAH: the mean concentrations of 1-NTP, 2-NTP, and 1-NP were 4.7, 1.9, and 32 pmol mg_DEP^–1, respectively. The mean 2-NTP/1-NTP, 1-NTP/1-NP, and 2-NTP/1-NP ratios in samples of airborne particles collected in a residential area in Osaka, Japan, were>1.55,<0.25, and 0.37, respectively; these values are much higher than those of the DEP samples. This finding indicates that there is another source for airborne NTPs, especially 2-NTP, apart from diesel exhaust. These results strongly suggest that airborne NTPs originate from atmospheric processes such as radical-initiated reactions of triphenylene, and this has a significant influence on the atmospheric occurrence of NTPs.     

Environmental occurrence of nitrotriphenylene observed in airborne particulate matter

1- and 2-Nitrotriphenylenes were found in the airborne particulate matter extracts collected in central Tokyo between the winter of 1998 and the winter of 1999. In particular, we have identified and quantified nitrotriphenylenes in the airborne particulate matter extracts collected over four consecutive 6-h periods on 2 December 1999. The concentrations of 1- and 2-nitrotriphenylene ranged from 0.04 to 0.44 and from 0.02 to 0.47 ng/m3, respectively, and the concentrations in the airborne particulate matter extracts collected during the 18:00-24:00 h time period were the highest of the four collection periods. 1-Nitropyrene and 2-nitrofluoranthene were also identified and quantified in the four 6-h samples. Although the concentrations of 1- and 2-nitrotriphenylenes were not higher than that of 2-nitrofluoranthene except during the 18:00-24:00 h time period, the concentrations were much higher than that of 1-nitropyrene during the four collection periods.The higher concentrations of 1- and 2-nitrotriphenylenes during the 18:00-24:00 h time period are presumably responsible for the high reactivity of parent triphenylene with NO2/NO3/N2O5, and high stability of 1- and 2-nitrotriphenylenes toward O3 + O2. In addition, the observed isomer distribution of nitrotriphenylenes suggested that direct emission of nitrotriphenylenes is also a source as well as their atmospheric formation.     

Determination of polycyclic aromatic hydrocarbons and substitutes (Nitro-, Oxy-PAHs) in urban soil and airborne particulate by GC-MS and NCI-MS/MS

A method involving high resolution gas chromatography combined with ion trap (HRGC-MS/MS) and negative chemical ionisation (NCI) was developed for the determination of nitrated or oxygenated polycyclic aromatic hydrocarbons (nitro-PAHs, oxy-PAHs) and other electrophilic substitutes in soil samples. Efficient clean-up was achieved by a combination of methods for the determination of PAHs in soil and nitro-PAHs in aerosol using solid phase extraction (SPE) and semipreparative high performance liquid chromatography (HPLC). In samples of surface soil from the city of Basle (Switzerland), nitro-PAHs (mainly 3-nitrofluoranthene and 1-nitropyrene) were found in concentrations between 30 and 800 ng/kg dry weight. Oxy-PAHs and parent PAHs revealed 10²-10⁴-fold higher levels. Nitro-PAHs which are up to 10⁵ times more mutagenic seem to be less persistent in soil than the parent forms, although their entire mutagenic potential has to be estimated as being on the same order of magnitude. In urban air particulate matter, the amounts of nitro-PAHs (2–62 pg/m³) were 10–100 times lower than oxyPAHs and parent PAHs which were both found in a similar range. 3-nitrobenzanthrone, a recently described suspected human carcinogen has not yet been detected. Using multivariate statistical analysis, it was possible to elucidate similarities or special characteristics of substances in a given matrix reflecting their chemical properties or specific emission sources.     

Heterogeneous reactions of ozone with pyrene, 1-hydroxypyrene and 1-nitropyrene adsorbed on particles

This work deals with the kinetic study of the reactions of ozone with pyrene, 1-hydroxypyrene and 1-nitropyrene, adsorbed on model particles. Experiments were performed at room temperature and atmospheric pressure, using a quasi-static flow reactor in the absence of light. Compounds were extracted from particles using pressurized fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different O₃ concentrations from which second order rate constants were calculated. The following rate constant values were obtained at 293 K: k(O₃ + Pyrene) = (3.2 ± 0.7) × 10^?16 cm³ molecule^?1 s^?1; k(O₃ + 1OHP) = (7.7 ± 1.4) ×10 ^?16 cm³ molecule^?1 s^?1; and k(O₃ + 1NP) = (2.2 ± 0.5) × 10^?17 cm³ molecule^?1 s^?1, for pyrene, 1-hydroxypyrene and 1-nitropyrene adsorbed on silica particles. The variation in the rate constants demonstrates the strong influence of the substituent (OH or NO₂) on the heterogeneous reactivity of pyrene. The pyrene particulate concentration was also varied in order to check how this parameter may influence the experiments. Finally, oxidation products were investigated for all reactions and some were detected and identified for the first time for ozone heterogeneous reaction with pyrene adsorbed on particles.     

Comparison of polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons in airborne particulates collected in downtown and suburban Kanazawa,Japan

In this study, airborne particulates were collected at three sites, two in a downtown area and the other in a suburban area of Kanazawa, Japan in each season for 7 years. Two polycyclic aromatic hydrocarbons (PAHs), pyrene (Py) and benzo[a]pyrene (BaP) and four nitropolycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (NP) and 1,3-, 1,6-, and 1,8-dinitropyrenes (DNP) were determined by high-performance liquid chromatography with fluorescence and chemiluminescence detection. At the downtown sites, the mean concentration of each DNP was about two orders of magnitude lower than that of 1-NP and more than three orders of magnitude lower than those of Py and BaP. This tendency reflected the composition of PAHs and NPAHs in diesel-engine exhaust particulates. Concentrations of these PAHs and NPAHs were higher at the downtown sites than at the suburban site, suggesting the dilution of these compounds during the transportation from the downtown to the suburban area. The concentration ratios of NPAHs to PAHs were larger at the downtown sites than at the suburban site. Studies using UV light and sunlight showed that degradation of NPAHs was faster than that of PAHs. Thus, the lower concentrations of NPAHs in the suburban sites may be due to their being photodegraded faster than PAHs during the atmospheric transportation from the downtown area to the suburban area.     

Determination and comparison of nitrated-polycyclic aromatic hydrocarbons measured in air and diesel particulate reference materials

The National Institute of Standards and Technology has issued numerous environmental matrix standard reference materials (SRMs) for the measurement of polycyclic aromatic hydrocarbons; however, only one SRM (diesel particulate material) was issued with certified and reference values for four nitrated-polycyclic aromatic hydrocarbons (nitro-PAH). The objective of this study was to develop an improved analytical procedure to quantify 28 mononitro- and dinitro-PAHs, including numerous isomers, in air and diesel particulate SRMs. Two air particulate matrix SRMs, SRM 1649a Urban Dust and SRM 1648 Urban Particulate Matter, and fine particulate matter, collected from Baltimore MD for use as an "interim reference material" for the determination of organic contaminants, have been characterized for nitro-PAHs. Concentrations of nitro-PAHs in all three air particulate materials were at the ng/g level with the highest nitro-PAH concentration being 2-nitrofluoranthene (range between 246 and 340 ng/g). For the three diesel particulate-related SRMs, SRM 1650a Diesel Particulate Matter, SRM 1975 Diesel Particulate Extract, and SRM 2975 Diesel Particulate Matter (Industrial Fortlift), concentrations of nitro-PAHs were in the microg/g range, with 1-nitropyrene as the dominant nitro-PAH (range between 18 and 40 microg/g). Distinct nitro-PAH isomer patterns were present between the air and diesel particulate materials. These results will provide isomer identification and reference concentrations for a large number of nitro-PAHs in the existing diesel and air particulate SRMs. Published by Elsevier Science Ltd.     

Association of the mutagenicity of airborne particles with the direct emission from combustion processes investigated in Osaka, Japan

The association of the direct-acting mutagenicity of soluble organic fraction of airborne particles toward Salmonella typhimurium YG1024 strain with the direct emission was investigated at a roadside and at a residential area in Osaka, Japan. The direct-acting mutagenicity was evaluated as mutagenic activity per unit volume of ambient air (rev m⁻³) and/or that per airborne particulate weight collected on a filter (rev mg⁻¹). The annual or diurnal changes of the mutagenicity of airborne particles at the residential site showed similar patterns to those of some gaseous pollutants such as NO₂ and SO₂, which were emitted from combustion processes. This result indicates that the mutagenicity is mainly attributable to the primary emissions. From the analysis of the relationship between the wind sector and the mutagenic intensity, rev m⁻³ and rev mg⁻¹ values were strongly affected by the emissions from the fixed sources and from the mobile sources, respectively. The rev m⁻³ value and concentration of 1-nitropyrene (1-NP) in unit per m³ at the roadside were a factor of 2.6 and 2.8 higher than those at the residential site, respectively, but the rev mg⁻¹ value and concentration of 1-NP in unit per mg at the roadside were substantially comparable to those at the residential area. These observations suggest that the characteristics of the airborne particles can be attributed to the automotive emissions even at the suburban area.     

Factors Influencing the Emissions of Nitrated-Polynuclear Aromatic Hydrocarbons(Nitro-PAH) from Diesel Engines

The potential problem of 1-nitropyrene (1-NP) formation during filter sampling of diesel emissions from dilution tubes is assessed. Rates of formation are calculated using data generated from several independent filter exposure studies. A portion of the 1-NP (12% average) found in participates collected from light-duty (LDD) and heavy-duty diesels (HOD) was found to be due to formation on the filter under average sampling conditions of 10-15/1 dilution at 44°C with 3 ppm NO₂ for 23 min. On the average, the concentration of 1-NP in participates emitted from HDD is 16 times less than that found in LDD run under similiar transient conditions. The average emission rate of 1-NP generated from the LDD and HDD was 4.7 μg/km and 1.5 μg/km, respectively for the vehicles operating under Federal Test Procedure (FTP)-transient conditions. Under operating conditions which increase exhaust temperature (increased speed and load), the concentration of nitro-PAH is significantly reduced with a concurrent increase in the concentration of partially oxidized nitro-PAH and dinitro-PAH. The concentration of 1-NP in the particulates measured from HDD in these dilution tube studies (0.33-0.95 ppm, depending upon engine load) is comparable to that measured in highway tunnel experiments (0.54 ppm average).     

Urban-Center CO Air Quality Projections

The distribution of mutagenic activity and nitroaromatic components of polycyclic organic matter (POM) in ambient air at industrial, urban, suburban, rural, and remote sites was studied using organic extracts from high volume aerosol samples. Direct-acting mutagens including 1-nitropyrene (1-NP), dinitropyrenes (DNP), and hydroxynitropyrenes (HNP) were measured by high performance liquid chromatography while the mutagenicity was determined in the Salmonella bioassay with strain TA-98. Benzo(a)pyrene (BaP), one of the possible precursors of nitroaromatic compounds in POM, was also measured. In comparing samples from a range of sites, TSP and the concentration of BaP per mass of particulate matter decreased, as expected, at greater distances from urban and industrial combustion sources. However, the concentrations of polar nitroaromatic POM compounds per mass of particles were higher at a remote site than in nonindustrial urban and suburban areas. The mutagenicity in particulate matter extracts from the remote area was predominantly (>90 percent) in the very polar fractions. There were also high atmospheric levels of nitroaromatic compounds and mutagenicity in heavily industrialized areas. These observations may reflect the influences of source emissions, atmospheric transformations of POM compounds, and ther atmospheric processes on the composition of ambient suspended particulate matter.     

Nitro-PAH formation studied by interacting artificially PAH-coated soot aerosol with NO2 in the temperature range of 295–523 K

Diesel particulate matter poses a threat to human health, and in particular nitrated polycyclic aromatic hydrocarbons (NPAHs) found within and on the surface of these particles. Although diesel particulate filters (DPFs) have been designed and implemented to reduce these and other harmful diesel emissions, the particle loaded filters may act as a reaction chamber for the enhanced production of NPAHs from the nitration of PAHs with NO₂.Focus is on the investigation of the heterogeneous reactions that occur on soot particles by exposing laboratory produced pyrene- or benzo(a)pyrene-coated spark discharge soot particles to varying concentrations of NO₂ and temperatures while following the formation of products over time. The sole nitration product that was observed throughout the experiments with pyrene-coated soot was 1-nitropyrene (1-NPYR), which increased linearly with reaction time for all NO₂ concentrations chosen (0.11, 1.0, 2.0, 4.0 ppm, m m^?1). Resulting 1-NPYR formation rate increased exponentially with [NO₂]. Throughout the 3-h experiments less than 10% of pyrene has been converted to 1-NPYR and the partial reaction order with regard to [NO₂] was estimated to 1.52. Benzo(a)pyrene (BaP) was more reactive than pyrene. After 3 h reaction time almost 80% of the BaP has been converted to 6-NBaP.Highest 1-NPYR concentrations on particles were detected at 373 K, and at higher temperatures a considerable decrease in particulate 1-NPYR was observed. A similar trend was observed in a DPF simulation system (PM-Kat^®-like) with BaP-coated soot. In this case, highest 6-NBaP concentration on particles was detected at 423 K. Backed by corroborating results from separate gas/solid-phase partition experiments with 1-NPYR and 6-NBaP, it is likely that the newly formed 1-NPYR and 6-NBaP became transferred from particle to gas phase at higher temperatures. Results from this study confirm the presence of 1-NPYR and 6-NBaP in particulate and gas phase under conditions encountered in DPFs, especially when operated at low temperature situations of the aftertreatment system.     

Relevant organic components in ambient particulate matter collected at Svalbard Islands (Norway)

n-Alkanes, polynuclear aromatic hydrocarbons and n-alkanoic acids present in the inhalable fraction of airborne particles have been determined at the Italian scientific base sited in the area of Ny Alesund, Spitzbergen Island, Norway. Both the profiles of n-alkane and polynuclear aromatic congeners among the respective classes showed that anthropogenic sources were responsible for the presence of particulate organics in the atmosphere there, since the monomodal distribution of aliphatics and the fresh-emission shape of PAH fraction were observed. The total contents of n-alkanes and PAH ranged from 19 to 97 ng m⁻³ and from 0.6 to 2.0 ng m⁻³, respectively; n-alkanoic acids reached 6 ng m⁻³. The occurrence of nitrated-PAH of photochemical origin at trace extent (i.e. nitrated-fluoranthenes and nitropyrenes) has been also observed. Since the occurrence of OH radicals is required together with NO_x for the processes leading to the generation of 2-nitrofluoranthene and 2-nitropyrene would start, the detection of these nitrated species revealed the occurrence of photochemical processes in that region.     

Heterogeneous reactivity of pyrene and 1-nitropyrene with NO2: Kinetics,product yields and mechanism

The heterogeneous reactivity of nitrogen dioxide with pyrene and 1-nitropyrene (1NP) adsorbed on silica particles has been investigated using a fast-flow-tube in the absence of light. Reactants and products were extracted from particles using pressurised fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different NO₂ concentrations and second order rate constants were calculated considering the oxidant concentration. The following rate constant values were obtained at room temperature: k(NO₂ + pyrene) = (9.3 ± 2.3) × 10^?17 cm³ molecule^?1 s^?1 and k(NO₂ + 1NP) = (6.2 ± 1.5) × 10^?18 cm³ molecule^?1 s^?1, showing that the reactivity of 1NP was slower by a factor of 15 than that of pyrene. 1NP was identified as the only NO₂-initiated oxidation product of pyrene and all the three dinitropyrenes were identified in the case of the 1NP reaction. The product quantification allowed showing that the kinetics of oxidation product formation was equal to that measured for parent compounds degradation, within uncertainties, confirming the validity of the reaction kinetics measurements.     

Photolysis of diclobutrazol in methanol

The fungicide diclobutrazol (2RS,3RS)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-ol was irradiated by ultra-violet light in methanol solution using (1) borosilicate glass apparatus and (2) quartz apparatus. The major differences observed were that photodegradation occurred more rapidly in (2) than (1) and more breakdown products were found in the former. Using g.c.-m.s. ten compounds were detected in (1) of which five were identified. In (2) twelve of the eighteen compounds observed were identified and the major component was 1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-one. The compounds reported were formed by oxidation, loss of chlorine or by cyclisation. This previously unreported cyclisation gave the s-triazolo-(5,1a)isoquinoline ring system.     

Experimental in situ chemical peroxidation of atrazine in contaminated soil

Lab-scale experiments of in situ chemical oxidation (ISCO), were performed on soil contaminated with 100 mg kg(-1) of atrazine (CIET). The oxidant used was hydrogen peroxide catalysed by naturally occurring minerals or by soluble Fe(II) sulphate, added in aqueous solution. The oxidation conditions were: CIET:H2O2=1:1100, 2 PV or 3 PV reaction volume, Fe(II):H2O2=0, 1:22, 1:11. Stabilized (with KH2PO4 at a concentration of 16 g l(-1)) or non-stabilized hydrogen peroxide was used. The pH of the reagents was adjusted to pH=1 with sulphuric acid, or was not altered. Results showed that the addition of soluble Fe(II) increased the temperature of the soil slurry and the use of stabilized hydrogen peroxide resulted in a lower heat generation. The treatment reduced the COD of the soil of about 40%, pH was lowered and natural organic matter became less hydrophobic. The highest atrazine conversion (89%) was obtained in the conditions: 3 PV, Fe(II):H2O2=1:11 with stabilized hydrogen peroxide added in two steps. The stabilizer only increased H2O2 life-time significantly when soluble Fe(II) was added. Results indicate as preferential degradation pathway of atrazine in soil dechlorination instead of dealkylation.     

Acceleration of catalase and peroxidase activities in Lemna minor L. and Allium cepa L. in response to low levels of aquatic mercury

The purpose of this study was to assess certain physiological responses of Lemna minor L. (duckweed) and Allium cepa L. (onion) to aquatic mercury at low concentrations. Following a 96-h exposure of plants to nutrient medium contaminated with known levels of mercuric chloride (HgCl(2)), 0.001 to 4 mg litre(-1) (0.0007 to 2.95 mg Hg litre(-1)) or methyl mercuric chloride (MeHgCl(2)), 0.0001 to 0.1 mg litre(-1) (0.0007 to 0.07 mg Hg litre(-1)), the physiological endpoints measured were the growth of fronds (Lemna minor) or roots (Allium cepa), and catalase and peroxidase activities in both plant assays. The EC(50) for HgCl(2) on the basis of the growth curve of Lemna minor was found to be 2.1 mg litre(-1). HgCl(2) and MeHgCl(2) were lethal to L. minor at concentrations of 4 and 0.01 mg litre(-1), respectively. The range of low concentrations that accelerated growth as well as enzymic activities in L. minor was 0.004 to 0.04 mg litre(-1) for HgCl(2) and 0.001 mg litre(-1) for MeHgCl(2). HgCl(2) and MeHgCl(2) induced maximum enzymic activity in Lemna fronds at concentrations of 0.008 and 0.0005 mg litre(-1), respectively. In Allium roots, catalase activity was accelerated at all the concentrations of HgCl(2) (0.001-2 mg litre(-1)) and MeHgCl(2) (0.0001-0.1 mg litre(-1)) tested. The activity of peroxidase was, however, accelerated by HgCl(2) at concentration range 0.01-1.0 mg litre(-1), or by MeHgCl(2) at 0.001 mg litre(-1). The concentrations of HgCl(2) and MeHgCl(2) that induced the highest enzymic activity in Allium roots were 0.05 mg litre(-1) and 0.001 mg litre(-1), respectively.     

Dry deposition of nitrogen and sulfur to Ponderosa and Jeffrey pine in the San Bernardino national forest in Southern California

Little is known about the concentrations, deposition rates, and effects of nitrogenous and sulfurous compounds in photochemical smog in the San Bernardino National Forest (SBNF) in southern California. Dry deposition of NO(3)(-) and NH(4)(+) to foliage of ponderosa pine (Pinus ponderosa Laws.) and Jeffrey pine (Pinus jeffreyi Grev. & Balf.) was correlated (R = 0.83-0.88) with historical average hourly O(3) concentations at 10 sites across an O(3) gradient in the SBNF. Mean deposition fluxes of NO(3)(-) to ponderosa and Jeffrey pine branches were 0.82 nmol M(-2)s(-1) at Camp Paivika (CP), a high-pollution site, and 0.19 nmol m(-2) s(-1) at Camp Osceola (CAO), a low-pollution site. Deposition fluxes of NH(4)(+) were 0.32 nmol m(-2) s(-1) at CP and 0.17 nmol m(-2) s(-1) at CAO, while mean values for SO(4)(2-) were 0.03 at CP and 0.02 nmol m(-2) s(-1) at CAO. Deposition fluxes to paper and nylon filters were higher in most cases than fluxes to pine branches at the same site. The results of this study suggest that an atmospheric concentration and deposition gradient of N and S compounds occurs along with the west-east O(3) gradient in the SBNF. Annual stand-level dry deposition rates for S and N at CP and CAO were estimated. Further studies are needed to determine if high N deposition loads in the SBNF significantly affect plant/soil nutrient relations, tree health, and the response of ponderosa pine to ozone.     

Human UDP-glucuronosyltransferase isoforms involved in bisphenol A glucuronidation

Bisphenol A (BPA) is one of a number of potential endocrine disruptors which may affect normal hormonal function. In this study, human UDP-glucuronosyltransferase (UGT) isoforms involved in BPA glucuronidation were studied by kinetic analyses using human liver microsomes and recombinant human UGTs expressed in insect cells (UGT1A1, UGT1A3, UGT1A4, UGT1A6, UGT1A9, UGT2B4, UGT2B7, UGT2B15 and UGT2B17). BPA glucuronidation was catalyzed by UGT1A1, UGT1A3, UGT1A9, UGT2B4, UGT2B7 and UGT2B15 as well as by human liver microsomes. Among these UGTs, UGT2B15 showed the highest activity of BPA glucuronidation at low- (1.0 microM) and high- (20 microM) substrate concentrations. Kinetic analyses of BPA glucuronidation were performed by constructing Michaelis-Menten and Eadie-Hofstee plots. The kinetic profile of BPA glucuronidation by pooled human liver microsomes and UGT2B15 was monophasic, the K(m) and V(max) values were 6.39 microM and 4250 pmol min(-1)mg(-1)protein for pooled human liver microsomes, and 8.68 microM and 873 pmol min(-1)mg(-1)protein for UGT2B15, respectively. The K(m) values for BPA glucuronidation by pooled human liver microsomes and UGT2B15 were similar. These findings demonstrate that BPA is mainly glucuronidated by UGT2B15 in human liver microsomes, and suggest that this UGT isoform plays important roles in the detoxification and elimination of BPA.     

Determining seasonal greenhouse gas emissions from ground-level area sources in a dairy operation in central Texas

Greenhouse gas (GHG) emissions from agricultural production operations are recognized as an important air quality issue. A new technique following the U.S. Environmental Protection Agency Method TO-14A was used to measure GHG emissions from ground-level area sources (GLAS) in a free-stall dairy operation in central Texas. The objective of this study was to quantify and report GHG emission rates (ERs) from the dairy during the summer and winter using this protocol. A weeklong sampling was performed during each season. A total of 75 and 66 chromatograms of air samples were acquired from six delineated GLAS (loafing pen, walkway, barn, silage pile, settling basin, and lagoon) of the same dairy during summer and winter, respectively. Three primary GHGs--methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O)--were identified from the dairy operation during the sampling periods. The estimated overall ERs for CH4, CO2, and N2O during the summer for this dairy were 274, 6005, and 7.96 g head(-1)day(-1), respectively. During the winter, the estimated overall CH4, CO2, and N2O ERs were 52, 7471, and 3.59 g head(-1)day(-1), respectively. The overall CH4 and N2O ERs during the summer were approximately 5.3 and 2.2 times higher than those in the winter for the free-stall dairy. These seasonal variations were likely due to fluctuations in ambient temperature, dairy manure loading rates, and manure microbial activity of GLAS. The annualized ERs for CH4, CO2, and N2O for this dairy were estimated to be 181, 6612, and 6.13 g head(-1)day(-1), respectively. Total GHG emissions calculated for this dairy with 500 cows were 2250 t of carbon dioxide equivalent (CO2e) per year.