Measurement of methyl halides in the marine atmosphere

An analytical method for measuring atmospheric methyl halides was established based on canister sampling and capillary GC/MS. Stability tests for air samples collected in two kinds of canisters (electro-chemical buffing and fused-silica lined) with smooth inner surfaces, showed that both provided stable storage for CH₃Cl, CH₃Br, and CH₃I. The method was applied to the measurement of methyl halides at a remote island (Okinawa, Japan) in August 1996, where nocturnal ozone depletion had been observed in summer. We found that atmospheric CH₃Cl increased during stable nights and was negatively correlated with surface ozone concentration. The highest CH₃Cl concentration amounted to as high as 1400 pptv and indicated that CH₃Cl emitted from the surrounding coastal areas had accumulated in the boundary layer under a stable atmosphere at that time. A positive correlation was observed between CH₃Br and CH₃I, suggesting a common source in the area.     

Extraction of chlorinated aliphatic hydrocarbons from groundwater at micromolar concentrations for isotopic analysis of chlorine.

A method is described for near-quantitative extraction of micromolar concentrations of chlorinated aliphatic hydrocarbons (CAHs) from water for determination of chlorine (Cl) isotope ratios. A low pressure, carrier-gas procedure of extraction was proven to be applicable to CH2Cl2, CCl4, C2H2Cl2, and C2HCl3. The pH of the water was adjusted with NaOH to prevent extraction of CO2 from air and/or dissolved inorganic carbonate species. Recoveries of CAH samples (approximately 15 mumol), added to and extracted from approximately 340 ml of water, averaged approximately 96%. Average changes in the delta 37Cl values of the CAHs, attributable to the extraction process, were -0.01 +/- 0.06@1000. Significant isotopic fractionation of Cl was measured during partial extraction of C2CHCl3 from water, indicating that near-quantitative extraction is required for reliable stable Cl isotope analysis of CAHs. This method is also suitable for the extraction of dissolved CAH for gas chromatography-combustion-isotope ratio mass spectrometric measurements of hydrogen and carbon.     

Atmospheric nitrous oxide: patterns of global change during recent decades and centuries

Data from weekly global measurements of nitrous oxide from 1981 to the end of 1996 are presented. The results show that there is more N2O in the northern hemisphere by about 0.7 +/- 0.04 ppbv, and the Arctic to Antarctic difference is about 1.2 +/- 0.1 ppbv. Concentrations at locations influenced by continental air are higher than at marine sites, showing the existence of large land-based emissions. For the period studied, N2O increased at an average rate of about 0.6 ppbv/year (approximately 0.2%/year) although there were periods when the rates were substantially different. Using ice core data, a record of N2O can be put together that goes back about 1000 years. It shows pre-industrial levels of about 287 +/- 1 ppbv and that concentrations have now risen by about 27 ppbv or 9.4% over the last century. The ice core data show that N2O started increasing only during the 20th century. The data presented here represent a comprehensive view of the present global distribution of N20 and its historical and recent trends.     

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.     

Comparison of atmosphere/aquatic environment concentration ratio of volatile chlorinated hydrocarbons between temperate regions and Antarctica

For the purpose of understanding the transport and deposition mechanisms and the air–water distribution of some volatile chlorinated hydrocarbons (VCHCs), their atmosphere/aquatic environment concentration ratio was evaluated. In addition, for the purpose of differentiating VCHC behaviour in a temperate climate from its behaviour in a polar climate, the atmosphere/aquatic environment concentration ratio evaluated in matrices from temperate zones was compared with the concentration ratio evaluated in Antarctic matrices.In order to perform air samplings also at rigid Antarctic temperatures, the sampling apparatus, consisting of a diaphragm pump and canisters, was suitably modified.Chloroform, 1,1,1-trichloroethane, tetrachloromethane, 1,1,2-trichloroethylene and tetrachloroethylene were measured in air, water and snow using specific techniques composed of a purpose-made cryofocusing-trap-injector (for air samples) and a modified purge-and-trap injector (for aqueous samples) coupled to a gas chromatograph with mass spectrometric detection operating in selected ion monitoring mode. The VCHCs were retrieved in all the investigated matrices, both Italian and Antarctic, with concentrations varying from tens to thousands of ng m⁻³ in air and from digits to hundreds of ng kg⁻¹ in water and snow.The atmosphere/aquatic environment concentration ratios were always found to be lower than 1. In particular, the Italian air/water concentration ratios were smaller than the Antarctic ones, by reason of the higher atmospheric photochemical activity in temperate zones. On the other hand, the Antarctic air/snow concentration ratios proved to be largely in favour of snow with respect to the Italian ratios, thus corroborating the hypothesis of a more efficient VCHC deposition mechanism and accumulation on Antarctic snow.     

Identification of methyl chloride-emitting plants and atmospheric measurements on a subtropical island

A survey of methyl chloride (CH3Cl)-emitting plants was performed at a subtropical island in Japan (Iriomote Island). Among the 187 species of tropical/subtropical plants investigated, 33 species from a variety of families were identified as CH3Cl-emitting plants. The strongest emitters were Osmunda banksiifolia, Cibotium balometz, Angiopteris palmiformis, Vitex rotundifolia, Vitex trifolia, and Excoecaria agalloch, each with CH3Cl emission rates exceeding 1microg (gdrywt)(-1)h(-1). The first three species are ferns, and the last three are halophilous plants. Based on our results, the character of CH3Cl emission is likely to be shared at the genus level but not always at the family level. The atmospheric CH3Cl distribution measured on Iriomote Island showed significant enhancement in forested sites (up to 2750 ppt) and a higher concentration on the downwind shore than on the upwind shore. As previously reported, our findings provide strong evidence for the high emission of CH3Cl from tropical/subtropical forests.     

Levels and pattern of volatile organic nitrates and halocarbons in the air at Neumayer Station (70 degrees S), Antarctic

Levels and patterns of C1-C4/C9 organic nitrates were measured for the first time in Antarctica. The sampling was done by adsorptive enrichment on Tenax TA followed by thermodesorption cold-trap high resolution capillary gas chromatography with electron capture detection. 2-70 1 air on-column have been analyzed this way. C1-C9 alkyl mononitrates, C2-C4 alkyl dinitrates, C2-C4 hydroxy alkyl nitrates, and halocarbons could be identified in air samples collected near the German Neumayer Research Station, Antarctica, in February 1999. Volatile biogenic and anthropogenic halocarbons were used to assess the origin of the air parcels analyzed. The average concentration measured for sigmaC2-C6 alkyl nitrates was in the range of 9.2 +/- 1.8 ppt(v), while the sum of the mixing ratios of six C2-C4 hydroxy alkyl nitrates was in the range of 1.1 +/- 0.2 ppt(v). Moreover, C2-C4 alkyl dinitrates were found at levels near the detection limit of 0.1-0.5 ppt(v). The concentrations of organic nitrates found in Antarctic air represent ultimate baseline levels due to chemical and physical loss processes during long-range transport in the air. The South Atlantic and the Antarctic Ocean as a general secondary source for organic nitrates in terms of an air/sea exchange equilibrium has to be evaluated yet, but it seems logical. Our results confirm the common assumption that there are no biogenic marine sources of C2-C9 organonitrates. We have found a level of > 80 ppt(v) for methyl nitrate. This level if it can be confirmed in a systematic survey requires a strong biogenic source of methyl nitrate in the Antarctic Ocean.     

Observed trends for CF3-containing compounds in background air at Cape Meares, Oregon, Point Barrow, Alaska, and Palmer Station, Antarctica

The concentrations of CF(3)-containing compounds in archived air samples collected at Cape Meares, Oregon, from 1978 to 1997, at Point Barrow, Alaska, from 1995 to 1998, and at Palmer Station, Antarctica, from 1991 to 1997, were determined by high resolution gas chromatography and high resolution mass spectrometry. The CF(3)-containing compounds measured by this method and discussed here are: the perfluorinated compound, C(3)F(8) (FC 218); four perhalogenated compounds, CF(3)Cl (CFC 13), CF(3)CF(2)Cl (CFC 115), CF(3)CFCl(2) (CFC 114a), and CF(3)Br (Halon 1301); and three hydrofluorocompounds, CF(3)H (HFC 23), CF(3)CH(3) (HFC 143a), and CF(3)CH(2)F (HFC 134a). For four of these compounds, very few measurements have been previously reported. The atmospheric concentrations of all of the CF(3)-containing compounds continuously increased in time over the sample collection periods. From these data, the annual rates of emission into the atmosphere have been estimated. The emission rates fall into one of three distinct categories. The annual emission rates of C(3)F(8), CF(3)H, CF(3)CH(3), and CF(3)CH(2)F have continuously increased over the last two decades. That of CF(3)CFCl(2) has decreased continuously. Emission rates for CF(3)Cl, CF(3)CF(2)Cl, and CF(3)Br reached maximum levels in the late 1980s, and have been decreasing in the 1990s. The emission rates of C(3)F(8), CF(3)CH(3) and CF(3)CH(2)F were nearly zero 20 years ago but have increased rapidly during the last decade.     

Concentrations and gas/particle partitioning of PCBs in Chicago

Thirty seven air samples were collected in Chicago, IL from June to October 1995 and analyzed for gas and particle concentrations of polychlorinated biphenyls (PCBs). Lower molecular weight (MW) PCBs dominated the samples and on average 95% of the Sigma50PCB concentration (gas+particulate) was in the vapor phase. Sigma50PCB concentrations were classified based on prevailing winds (lake and land). The Sigma50PCB concentration varied between 0.42 and 5.21 ng/m3 (1.80+/-1.70 ng/m3) for lake and 0.53 and 8.31 ng/m3 (2.41+/-2.15 ng/m3) for land wind directions. Back trajectory analyses suggested that SW of Chicago can be an important local or regional source sector for PCBs. Partitioning between gas and particulate phases was modeled using the Junge-Pankow model. The measured particle phase concentrations for low MW PCBs were lower than those predicted by the model while the opposite was observed for high MW PCBs. Plots of gas/particle partition coefficient (log Kp) vs. subcooled liquid vapor pressure (log pL(0)) had reasonable correlations for individual samples but the slope varied among the samples. Samples that originated from over the lake had higher slopes than samples that originated from over the land.     

Monitoring of reduced sulfur compounds in the atmosphere of Gosan, Jeju Island during the Spring of 2001

The atmospheric concentrations of dimethylsulfide (DMS) and carbon disulfide (CS2) were measured concurrently with relevant environmental parameters at Gosan, Jeju Island, Korea during 5-26 April 2001. The mean concentrations for these two compounds were 18.7+/-17.9 and 6.4+/-9.9 pptv, respectively. Results of our analysis indicated that relative temporal variations between DMS and CS2 can be best described by dividing the whole data set into three different periods which reflect the variable transport patterns of air masses into the study area. (Periods I, II, and III denote: 5-10, 10-18, and 19-26 April.) The environmental conditions during those three periods varied greatly. The effects of continental and/or oceanic processes were evident for certain periods, yielding diverse relationships between DMS and CS2 in both absolute and relative terms. Most observed variations were best explained in terms of an interplay between source/sink processes and air mass transport patterns. The sea-to-air flux of DMS, when estimated using our measurement data during this study period, was approximately 4 micromole m(-2)d(-1).     

PCDD/F and dioxin-like PCB in Hong Kong air in relation to their regional transport in the Pearl River Delta region

PCDD/F and dioxin-like PCB were measured in 142 air samples of Hong Kong. The annual average PCDD/F and dioxin-like PCB concentrations obtained for Hong Kong air at Tap Mun (PCDD/F: 1724+/-1984; dioxin-like PCB: 1572+/-1170 fg m(-3)), Yuen Long (PCDD/F: 2927+/-2695; dioxin-like PCB: 4331+/-1962 fg m(-3)) and Tsuen Wan (PCDD/F: 1875+/-1502; dioxin-like PCB: 2972+/-1510 fg m(-3)) from January 2004 to March 2005 were comparable to other urban centers around the world and were within the Japanese and USA ambient air quality guidelines. A clear seasonal pattern was observed for PCDD/F, generally with a 50-60 times higher air concentration in winter when background northerly wind was weaker and land-sea breeze prevailed, resulting in regional transport; and a lower concentration in summer, due to the inflow of clean oceanic southeasterly wind from the South China Sea. A higher WHO-TEQ value of dioxin-like PCB (mainly attributed to the relatively higher WHO-TEQ value of PCB 126) in Yuen Long during winter, compared with other months, could also be related to the regional transport by the winter monsoon wind and the low mixing height in winter. Spatially, air concentrations of PCDD/F and dioxin-like PCB demonstrated a west-to-east gradient (with Yuen Long>Tsuen Wan>Tap Mun). It is suggested that PCDD/F and dioxin-like PCB were transported into the western airshed of Hong Kong from the Pearl River Delta by land-sea breeze circulation and confined to the northwestern part, due to the blocking effect of the northwestern airshed in Hong Kong.     

Direct VUV photolysis of chlorinated methanes and their mixtures in a nitrogen stream

The gas-phase decomposition of CCl(4), CHCl(3) and CH(2)Cl(2) and their binary mixtures was studied in a flow-type reactor in a nitrogen gas stream, using a low-pressure mercury vapour lamp covered with a high-purity silica quartz sleeve. The 184.9 nm vacuum-ultraviolet (VUV) light emitted is able to rupture the C-Cl bond in these target substances. For H-containing compounds, the decomposition takes place not only by direct photolysis, but also by H abstraction by .Cl formed during the direct photolysis of the target substances. The relative contributions of direct photolysis and .Cl-sensitized reactions to the decomposition were estimated at different initial concentrations. The addition of CCl(4) to CHCl(3) or CH(2)Cl(2) increased their decomposition rates via increase of the .Cl concentration, whereas the addition of CH(2)Cl(2) to CHCl(3) decreased its degradation rate, suggesting that CH(2)Cl(2) acts as a .Cl radical scavenger. The variation of the product distribution confirms the effect of the composition of the irradiated gas mixtures on the relative contributions of .Cl-sensitized reactions and direct photolysis.     

Catalytic destruction of dichloromethane using perovskite-type oxide catalysts

Dichloromethane (DCM, also known as methylene chloride [CH2Cl2]) is often present in industrial waste gas and is a valuable chemical product in the chemical industry. This study addresses the oxidation of airstreams that contain CH2Cl2 by catalytic oxidation in a tubular fixed-bed reactor over perovskite-type oxide catalysts. This work also considers how the concentration of influent CH2Cl2 (Co = 500-1000 ppm), the space velocity (GHSV = 5000-48,000 1/hr), the relative humidity (RH = 10-70%) and the concentration of oxygen (O2 = 5-21%) influence the operational stability and capacity for the removal of CH2Cl2. The surface area of lanthanum (La)-cobalt (Co) composite catalyst was the greatest of the five perovskite-type catalysts prepared in various composites of La, strontium, and Co metal oxides. Approximately 99.5% CH2Cl2 reduction was achieved by the catalytic oxidation over LaCoO3-based perovskite catalyst at 600 degrees C. Furthermore, the effect of the initial concentration and reaction temperature on the removal of CH2Cl2 in the gaseous phase was also monitored. This study also provides information that a higher humidity corresponds to a lower conversion. Carbon dioxide and hydrogen chloride were the two main products of the oxidation process at a relative humidity of 70%.     

The distinctive isotopic signature of plant-derived chloromethane: possible application in constraining the atmospheric chloromethane budget

Chloromethane (CH(3)Cl) is the most abundant halocarbon in the atmosphere. Although largely of natural origin it is responsible for around 17% of chlorine-catalysed ozone destruction. Sources identified to date include biomass burning, oceanic emissions, wood-rotting fungi, higher plants and most recently tropical ferns. Current estimates reveal a shortfall of around 2 million ty(-1) in sources versus sinks for the halocarbon. It is possible that emissions from green plants have been substantially underestimated. A potentially valuable tool for validating emission flux estimates is comparison of the delta13C value of atmospheric CH(3)Cl with those of CH(3)Cl from the various sources. Here we report delta13C values for CH(3)Cl released by two species of tropical ferns and show that the isotopic signature of CH(3)Cl from pteridophytes like that of CH(3)Cl from higher plants is quite different from that of CH(3)Cl produced by biomass burning, fungi and industry. delta13C values for CH(3)Cl produced by Cyathea smithii and Angiopteris evecta were respectively -72.7 per thousand and -69.3 per thousand representing depletions relative to plant biomass of 42.3 per thousand and 43.4 per thousand. The characteristic isotopic signature of CH(3)Cl released by green plants should help constrain their contribution to the atmospheric burden when reliable delta13C values for all other major sources of CH(3)Cl are obtained and a globally averaged delta13C value for atmospheric CH(3)Cl is available.     

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.     

Bulk deposition of polycyclic aromatic hydrocarbons (PAHs) in an industrial site of Turkey

Ambient air and deposition samples were collected in the period of July 2004-May 2005 in an industrial district of Bursa, Turkey and analyzed for polycyclic aromatic hydrocarbon (PAH) compounds. The overall average of fourteen bulk deposition fluxes for PAHs was 3300+/-5100 ng m(-2) d(-1). PAH depositions showed a seasonal variation and they were higher in winter months. This was probably due to increases in residential heating activities and decreases in atmospheric mixing layer levels. Ambient air samples, measured with a high volume air sampler, were collected from the same site. The average total concentration including gas and particulate phase was about 300+/-420 ng m(-3) and it was in the range of previously reported values. Some of the ambient air and bulk deposition samples were collected simultaneously in dry periods. Both concurrently measured values were used to calculate the dry deposition velocities whose overall average value was 0.45+/-0.35 cm s(-1).     

Contribution of winter to the annual CH4 emission from a eutrophied boreal lake

The springtime methane (CH4) emission from a small, eutrophied boreal lake was assessed during the winter ice-cover by measurement of gas ebullition and CH4 accumulation in the water column in association with the development of oxygen depletion after ice formation. The winter CH4 production was estimated to result in a loss of 3.6-7.9 g CH4 m(-2) from the lake to the atmosphere during the short period of ice melt. This could account for 22-48% of the annual CH4 emission from the pelagic zone of the lake. The contribution of winter to the annual CH4 release can be similar or even higher in seasonally ice-covered northern aquatic ecosystems than in northern terrestrial wetlands, thus winter must be considered in any studies into the aquatic CH4 emissions. The trophic state and wintertime oxygen conditions, linked to the changes in land-use in the catchments and climate, are important factors controlling the springtime lake CH4 emissions.     

Formate,acetate and methanesulfonate measurements in antarctic ice: Some geochemical implications

Serious contamination problems are encountered when measuring organic acids in polar ice. Using an involved experimental protocol, methanesulfonate, formate and acetate have been investigated in ice core sections from Antarctica. With CH₃SO₃⁻ concentrations of a few ppb, HCOO⁻at a few tenths of ppb and CH₃COO⁻ around our detection limit, the organic acids represent only a small percentage of the total acidity in Antarctic ice.Analysis of the various possible sources indicates that methane is probably the major atmospheric precursor (via formaldehyde) of formate present in the ice.The significant presence of CH₃SO₃⁻ in Antarctic ice confirms the preponderant role played by marine biogenic emissions in the Antarctic sulfate budget. The CH₃SO₃⁻ ratio with respect to non-sea-salt sulfate is higher in Antarctic precipitation than in marine aerosol. Finally, CH₃SO₃⁻ in polar ice is suggested to be a more suitable parameter than excess sulfate for the study of marine biogenic emissions in the past.     

Carbonyl sulfide,dimethyl sulfide and carbon disulfide in the Pearl River Delta of southern China: Impact of anthropogenic and biogenic sources

Reduced sulfur compounds (RSCs) such as carbonyl sulfide (OCS), dimethyl sulfide (DMS) and carbon disulfide (CS₂) impact radiative forcing, ozone depletion, and acid rain. Although Asia is a large source of these compounds, until now a long-term study of their emission patterns has not been carried out. Here we analyze 16 months of RSC data measured at a polluted rural/coastal site in the greater Pearl River Delta (PRD) of southern China. A total of 188 canister air samples were collected from August 2001 to December 2002. The OCS and CS₂ mixing ratios within these samples were higher in autumn/winter and lower in summer due to the influence of Asian monsoon circulations. Comparatively low DMS values observed in this coastal region suggest a relatively low biological productivity during summer months. The springtime OCS levels in the study region (574 ± 40 pptv) were 25% higher than those on other East Asia coasts such Japan, whereas the springtime CS₂ and DMS mixing ratios in the PRD (47 ± 38 pptv and 22 ± 5 pptv, respectively) were 3–30 times lower than elevated values that have been measured elsewhere in East Asia (Japan and Korea) at this time of year. Poor correlations were found among the three RSCs in the whole group of 188 samples, suggesting their complex and variable sources in the region. By means of backward Lagrangian particle release simulations, air samples originating from the inner PRD, urban Hong Kong and South China Sea were identified. The mean mixing ratio of OCS in the inner PRD was significantly higher than that in Hong Kong urban air and South China Sea marine air (p < 0.001), whereas no statistical differences were found for DMS and CS₂ among the three regions (p > 0.05). Using a linear regression method based on correlations with the urban tracer CO, the estimated OCS emission in inner PRD (49.6 ± 4.7 Gg yr^?1) was much higher than that in Hong Kong (0.32 ± 0.05 Gg yr^?1), whereas the estimated CS₂ and DMS emissions in the study region accounted for a very few percentage of the total CS₂ and DMS emission in China. These findings lay the foundation for better understanding sulfur chemistry in the greater PRD region of southern China.     

Atmospheric peroxides over the North Pacific during IOC 2002 shipboard experiment

Atmospheric hydrogen peroxide and methyl hydroperoxide were determined onboard the Melville over the North Pacific from Osaka to Honolulu during May-June 2002. The concentrations of H(2)O(2) and CH(3)OOH increased from 0.64+/-0.57 ppbv and 0.27+/-0.59 ppbv in subpolar region (30-50 degrees N) to 1.96+/-0.95 ppbv and 1.56+/-1.3 ppbv in subtropical region (24-30 degrees N). The increase in concentrations towards the Equator was more pronounced for CH(3)OOH than H(2)O(2). In contrast, the levels of O(3) and CO were decreased at lower latitudes as air mass was more aged, denoted by the ratios of C(2)H(2)/CO and C(3)H(8)/C(2)H(6). CH(3)OOH concentrations showed a clear diurnal variation with a maximum around noon and minimum before sunrise. Frequently, the concentrations of peroxides remained over 1 ppbv in the dark and even gradually increased after sunset. In addition, the ratios of C(2)H(4)/C(2)H(6) and C(3)H(6)/C(3)H(8) were increased in aged subtropical air, which implies that these alkenes were emitted from the ocean surface. As a result, the reaction of these biogenic alkenes with O(3) was suggested to be a potential source for peroxides in aged marine air at lower latitudes.