Gaseous and Particulate Oxidation Products Analysis of a Mixture of α-pinene + β-pinene/O3/Air in the Absence of Light and α-pinene + β-pinene/NOx/Air in the Presence of Natural Sunlight

The gas and particle phase reaction products of a mixture of the atmospherically important terpenes -pinene and -pinene with the atmospheric oxidants O₃ and OH/NO_x were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of a mixture of -pinene and -pinene in the presence of O₃/air, and the daytime oxidation of a mixture of -pinene + -pinene with NO_x air in the presence of natural sunlight were carried out in the University of North Carolina's large outdoor smog chamber (190 m³) located in Chatham County, North Carolina. Mass balances for gaseous and aerosol reaction products are reported over the course of the reaction. More than twenty-nine products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 74 to 80% of the reacted -pinen/-pinene mixture carbon. Measurements show that a number of reaction products were found in both O₃ and NO_x system [pinonaldehyde, pinic acid, pinonic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxy-nopinone, 3-hydroxy-nopinone, and nopinone]. Pinonic acid, pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, and 10-hydroxypinonic acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols.     

Gas and Particulate Products Distribution from the Photooxidation of α-Humulene in the Presence of NOx, Natural Atmospheric Air and Sunlight

The photooxidation of -humulene in the presence of NO_x, natural sunlight, and rural background air was investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). Identification and quantification of gas and particulate reaction products were reported over the course of the reaction. The daytime photooxidation was carried out in a large outdoor smog chamber (190 m³). A wide range of ring retaining and ring opening products in the gas and particle phase are reported. On average, measured gas and particle phase products accounted for 44% of the reacted -humulene carbon. Measurements show that a number of reaction products with low vapor pressures (e.g. 3-seco--humulone aldehyde, 7-seco--humulone aldehyde, -humulal aldehyde, -humulene 3-oxide or -humulene 7-oxide, -humulaic/alic acid isomers, and 3-seco--14-hydroxyhumulone aldehyde) were found in the early stage of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.     

Products and Mechanism of the Gas Phase Reaction of Ozone with β-Pinene

Gas phase ozonolysis of -pinene was performedin a 570 l static reactor at 730 Torr and 296 K insynthetic air and the products were analysed by acombination of gas phase FTIR spectroscopy, HPLC andIC analyses of gas phase and aerosol samples,respectively. The reaction mechanism was investigatedby adding HCHO, HCOOH and H₂O as Criegeeintermediate scavenger and cyclohexane as OH radicalscavenger. Main identified products (yields inparentheses) in the presence of cyclohexane as OHradical scavenger were HCHO (0.65 ± 0.04),nopinone (0.16 ± 0.04), 3-hydroxy-nopinone (0.15± 0.05), CO₂ (0.20 ± 0.04), CO (0.030± 0.002), HCOOH (0.020 ± 0.002), the secondaryozonide of -pinene (0.16 ± 0.05), andcis-pinic acid (0.02 ± 0.01). The decompositionof the primary ozonide was found to yieldpredominantly the excited C₉-Criegee intermediateand HCHO (0.84 ± 0.04) and to a minor extent theexcited CH₂OO intermediate and nopinone (0.16± 0.04). Roughly 40% of the excitedC₉-Criegee intermediate becomes stabilised andcould be shown to react with HCHO, HCOOH and H₂O. The atmospherically important reaction of thestabilised C₉-Criegee intermediate with H₂Owas found to result in a nopinone increase of (0.35± 0.05) and in the formation of H₂O₂(0.24 ± 0.03). Based on the observed products,the unimolecular decomposition/isomerisationchannels of the C₉-Criegee intermediate arediscussed in terms of the hydroperoxide and esterchannels. Subsequent reactions of the nopinonylradical, formed in the hydroperoxide channel, lead tomajor products like 3-hydroxy-nopinone but also tominor products like cis-pinic acid. A mechanismfor the formation of this dicarboxylic acid isproposed and its possible role in aerosol formationprocesses discussed.     

Gas and Particle Products Distribution from the Reaction of β-Caryophyllene with Ozone

Gas and particulate reaction products from the ozonolysis of -caryophyllene (I) in the presence of atmospheric air were investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). A Scanning Mobility Particle Sizer system (3936, TSI) and a Condensation Particle Counter (3025A, TSI) were used to study secondary organic aerosol formation. The nighttime oxidation was carried out in a large outdoor smog chamber (190 m³). A wide range of ring retaining and ring opening products in the gas and particle phase are reported over the course of the reaction. On average, measured gas and particle phase products accounted for 64% of the reacted -caryophyllene (I) carbon. Measurements show that a number of reaction products with low vapor pressure (e.g., -caryophyllone aldehyde (IV), -norcaryophyllone aldehyde (V), -caryophyllonic acid (VIII), -14-hydroxycaryophyllonic acid (XIV)) were found in the sample taken during the first 20 min of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.     

The Influence of O3, Relative Humidity, NO and NO2 on the Oxidation of α-Pinene and Δ3-Carene

Upto 13% of -pinene and ³-carene had reacted after 213 s in this dark experimental set-up, where O₃, NO and NO₂ were mixed with terpenes at different relative humidities (RHs). The different experiments were planned according to an experimental design, where O₃, NO₂, NO, RH and reaction time were varied between high and low settings (25 and 75 ppb, 15 and 42%, 44 and 213 s). An increased amount of -pinene and ³-carene reacted in the chamber was observed, when the level of O₃, NO and reaction time was increased and RH was decreased. In the study, it was found that different interactions affected the amount of terpene reacted as well. These interactions were between O₃ and NO, O₃ and reaction time, NO and RH, and between NO and reaction time.     

Is the Arctic Surface Layer a Source and Sink of NOx in Winter/Spring?

Measurements of NO_x (NO +NO₂) and the sum of reactive nitrogenconstituents, NO_y, were made near the surface atAlert (82.5°N), Canada during March and April1998. In early March when solar insolation was absentor very low, NO_x mixing ratios were frequentlynear zero. After polar sunrise when the sun was abovethe horizon for much or all of the day a diurnalvariation in NO_x and NO_y was observed withamplitudes as large as 30–40 pptv. The source ofactive nitrogen is attributed to release from the snowsurface by a process that is apparently sensitized bysunlight. If the source from the snowpack is a largescale feature of the Arctic then the diurnal trendsalso require a competing process for removal to thesurface. From the diurnal change in the NO/NO₂ratio, mid-April mixing ratios for the sum of peroxyand halogen oxide radicals of 10 pptv werederived for periods when ozone mixing ratios were inthe normal range of 30–50 ppbv. Mid-day ozoneproduction and loss rates with the active nitrogensource were estimated to be 1–2 ppbv/day and in nearbalance. NO_y mixing ratios which averaged only295±66 pptv do not support a large accumulation inthe high Arctic surface layer in the winter and springof 1998. The small abundance of NO_y relative tothe elevated mixing ratios of other long-livedanthropogenic constituents requires that reactivenitrogen be removed to the surface during transport toor during residence within the high Arctic.     

Drought history inferred from tree ring δ 13C and δ 18O in the central Tianshan Mountains of China and linkage with the North Atlantic Oscillation

Annual tree ring δ ¹⁸O and δ ¹³C chronologies from 1790 to 2008 were established using Tianshan spruce (Picea schrenkiana) in the central Tianshan Mountains of northwestern China. Temperature has a positive effect on tree ring δ ¹⁸O and δ ¹³C in the study area, while precipitation and relative humidity have negative effects. The standardized precipitation–evapotranspiration index (SPEI) considered all of these effects and was significantly negatively correlated with tree ring δ ¹⁸O and δ ¹³C. We combined the tree ring δ ¹⁸O and δ ¹³C series to reconstruct the past 192 years of SPEI, which accounted for about 46 % of the total variance of SPEI from 1950 to 2006. The reconstruction showed good spatial agreement with gridded data in Palmer Drought Severity Index and precipitation and an inverse relationship with temperature. Our SPEI reconstruction reveals several wet and dry periods over the past 192 years and has good agreement with other drought records. Wavelet analysis showed quasi-periodic 10-, 20-, 30-, and 70-year fluctuations in the reconstruction. The 10-, 20-, and 30-year periodicities may reflect the potential influence of North Atlantic Oscillation (NAO). Overall, this study indicates that the SPEI is a potential drought index, and the winter NAO affects regional moisture conditions in the long term.     

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

Infra‐red FTS measurements of CH4, N2O,O3, HNO3, HCl,CFC‐11 and CFC‐12 from the MANTRA balloon campaign

Abstract

The Middle Atmosphere Nitrogen TRend Assessment (MANTRA) campaign is intended to address the question of whether possible changes in the mid‐latitude nitrogen budget can account for discrepancies between predicted and observed ozone loss at these latitudes. In addition, MANTRA seeks to establish consistency between old and new measurement techniques. We report here the results of infra‐red spectral measurements made with a high resolution Fourier Transform Spectrometer (FTS) during the August 1998 MANTRA flight. Vertical mixing ratio profiles of methane, nitrous oxide, ozone, nitric acid, hydrogen chloride, CFC‐11 and CFC‐12 are presented. The error estimates on the retrieved values are larger than typical for this type of measurement, due mostly to instrument problems that occurred during flight. In addition, the CFC values are larger than expected. Possible reasons for this are discussed.     

Development of regional future climate change scenarios in South America using the Eta CPTEC/HadCM3 climate change projections: climatology and regional analyses for the Amazon, S?o Francisco and the Paraná River basins

The objective of this study is to assess the climate projections over South America using the Eta-CPTEC regional model driven by four members of an ensemble of the Met Office Hadley Centre Global Coupled climate model HadCM3. The global model ensemble was run over the twenty-first century according to the SRES A1B emissions scenario, but with each member having a different climate sensitivity. The four members selected to drive the Eta-CPTEC model span the sensitivity range in the global model ensemble. The Eta-CPTEC model nested in these lateral boundary conditions was configured with a 40-km grid size and was run over 1961–1990 to represent baseline climate, and 2011–2100 to simulate possible future changes. Results presented here focus on austral summer and winter climate of 2011–2040, 2041–2070 and 2071–2100 periods, for South America and for three major river basins in Brazil. Projections of changes in upper and low-level circulation and the mean sea level pressure (SLP) fields simulate a pattern of weakening of the tropical circulation and strengthening of the subtropical circulation, marked by intensification at the surface of the Chaco Low and the subtropical highs. Strong warming (4–6°C) of continental South America increases the temperature gradient between continental South America and the South Atlantic. This leads to stronger SLP gradients between continent and oceans, and to changes in moisture transport and rainfall. Large rainfall reductions are simulated in Amazonia and Northeast Brazil (reaching up to 40%), and rainfall increases around the northern coast of Peru and Ecuador and in southeastern South America, reaching up to 30% in northern Argentina. All changes are more intense after 2040. The Precipitation–Evaporation (P–E) difference in the A1B downscaled scenario suggest water deficits and river runoff reductions in the eastern Amazon and S?o Francisco Basin, making these regions susceptible to drier conditions and droughts in the future.