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Aim: We are using the fossil record of different marine plankton groups to determine how their biodiversity has changed during past climate warming comparable to projected future warming. Location: North Atlantic Ocean and adjacent seas. Time series cover a latitudinal range from 75° N to 6° S. Time period: Past 24,000 years, from the Last Glacial Maximum (LGM) to the current warm period covering the last deglaciation. Major taxa studied: Planktonic foraminifera, dinoflagellates and coccolithophores. Methods: We analyse time series of fossil plankton communities using principal component analysis and generalized additive models to estimate the overall trend of temporal compositional change in each plankton group and to identify periods of significant change. We further analyse local biodiversity change by analysing species richness, species gains and losses, and the effective number of species in each sample, and compare alpha diversity to the LGM mean. Results: All plankton groups show remarkably similar trends in the rates and spatio‐temporal dynamics of local biodiversity change and a pronounced non‐linearity with climate change in the current warm period. Assemblages of planktonic foraminifera and dinoflagellates started to change significantly with the onset of global warming around 15,500 to 17,000 years ago and continued to change at the same rate during the current warm period until at least 5000 years ago, while coccolithophore assemblages changed at a constant rate throughout the past 24,000 years, seemingly irrespective of the prevailing temperature change. Main conclusions: Climate change during the transition from the LGM to the current warm period led to a long‐lasting reshuffling of zoo‐ and phytoplankton assemblages, likely associated with the emergence of new ecological interactions and possibly a shift in the dominant drivers of plankton assemblage change from more abiotic‐dominated causes during the last deglaciation to more biotic‐dominated causes with the onset of the Holocene. [ABSTRACT FROM AUTHOR]

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16-36% of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼ 100μgm-3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0±2.0 × 10-13cm3molec-1s-1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 1012molec cm-3s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH = 0.59±0.33 in SE US and γOH = 0.68±0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.

The emission, dispersion, and photochemistry of isoprene (C5H8) and related chemical species in the convective boundary layer (CBL) during sunlit daytime were studied over a mixed forest in the southeastern United States by combining ground-based and aircraft observations. Fluxes of isoprene and monoterpenes were quantified at the top of the forest canopy using a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). Snapshot (2 min sampling duration) vertical profiles of isoprene, methyl vinyl ketone (MVK)Cmethacrolein (MACR), and monoterpenes were collected from aircraft every hour in the CBL (100-1000 m). Both ground-based and airborne collected volatile organic compound (VOC) data are used to constrain the initial conditions of a mixed-layer chemistry model (MXLCH), which is applied to examine the chemical evolution of the O3-NOx-HOx-VOC system and how it is affected by boundary layer dynamics in the CBL. The chemical loss rate of isoprene (1 h) is similar to the turbulent mixing timescale (0.1-0.5 h), which indicates that isoprene concentrations are equally dependent on both photooxidation and boundary layer dynamics. Analysis of a modelderived concentration budget suggests that diurnal evolution of isoprene inside the CBL is mainly controlled by surface emissions and chemical loss; the diurnal evolution of O3 is dominated by entrainment. The NO to HO2 ratio (NO :HO2) is used as an indicator of anthropogenic impact on the CBL chemical composition and spans a wide range (1-163). The fate of hydroxyl-substituted isoprene peroxyl radical (HOC5H8OO q; ISOPOO) is strongly affected by NO:HO2, shifting from NO-dominant to NO-HO2-balanced conditions from early morning to noontime. This chemical regime change is reflected in the diurnal evolution of isoprene hydroxynitrates (ISOPN) and isoprene hydroxy hydroperoxides (ISOPOOH).

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NOx environments. Production and loss of IN have a significant influence on the NOx cycle and tropospheric O3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/-3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (∼ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.

We report measurements of ambient amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a southeastern US forest and a moderately polluted midwestern site during the summer. At the forest site, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected, and they both showed temperature dependencies. Aerosol-phase amines measured thermal-desorption chemical ionization mass spectrometer (TDCIMS) showed a higher mass fraction in the evening with cooler temperatures and lower in the afternoon with warmer temperatures, a trend opposite to the gas-phase amines. Concentrations of aerosol-phase primary amines measured with Fourier transform infrared spectroscopy (FTIR) from micron and submicron particles were 2 orders of magnitude higher than the gas-phase amines. These results indicate that gas to particle conversion is one of the major processes that control the ambient amine concentrations at this forest site. Temperature dependencies of C3-amines and ammonia also imply reversible processes of evaporation of these nitrogen-containing compounds from soil surfaces in daytime and deposition to soil surfaces at nighttime. During the transported biomass burning plume events, various amines (C1-C6) appeared at the pptv level, indicating that biomass burning is a substantial source of amines in the southeastern US. At the moderately polluted Kent site, there were higher concentrations of C1- to C6-amines (pptv to tens of pptv) and ammonia (up to 6 ppbv). C1- to C3-amines and ammonia were well correlated with the ambient temperature. C4- to C6-amines showed frequent spikes during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Higher amine concentrations measured at the polluted site than at the rural forested site highlight the importance of constraining anthropogenic emission sources of amines.

We present measurements of trace gases and fine aerosols obtained from a rural site in eastern China during 18 February to 30 April 2001. The field program aimed to characterize the variations in aerosol and gaseous pollutant concentrations and the emission signatures from the inland region of eastern China in the spring season. The data included O3, CO, NO, NOy*, SO2, methane, C2-C8 nonmethane hydrocarbons (NMHCs), C 1-C2 halocarbons, and the chemical composition of PM2.5. The average hourly mixing ratios (±standard deviation) of CO, SO2, and NOy* were 677 (±315) ppbv, 15.9 (±14.6) ppbv, and 13.8 (±7.2) ppbv, respectively. The mean daytime ozone mixing ratio was 41 (± 19) ppbv. The most abundant NMHC was ethane (3189 ± 717 pptv), followed by ethyne (2475 ± 1395 pptv), ethene (1679 ± 1455 pptv), and toluene (1529 ± 1608 pptv). Methyl chloride was the most abundant halocarbon (1108 ± 653 pptv). The average concentrations of particulate organic matter (POM, as organic carbon, OC, times 1.4) and elemental carbon (EC) in PM2.5 were 21.5 (±7) μg/m3 and 2.5 (±0.7) μg/m3, respectively, and sulfate and nitrate levels were 17.3 (±6.6) and 6.5 (±4) μg/m3, respectively. CO showed moderate to good correlation with NOy* (r2 = 0.59), OC (r2 = 0.65), CH3Cl (r2 = 0.59), soluble potassium (r2 = 0.53), and many NMHCs, indicating contributions from the burning of biofuel/biomass. CO also correlated with an industrial tracer, C2Cl4, indicative of some influence from industrial sources. SO2, on the other hand, correlated well with EC (r2 = 0.56), reflecting the contribution from the burning of coal. Ammonium was sufficiently abundant to fully neutralize sulfate and nitrate, indicating that there were strong emissions of ammonia from agricultural activities. Silicon and calcium had poor correlations with iron and aluminum, revealing the presence of source(s) for Si and Ca other than from soil. Examination of C2H2/CO, C3H8/C 2H6, nitrate/(nitrate + NOy* , and sulfate/(SO2 + sulfate) suggested that relatively fresh air masses had been sampled at the study site in the spring season. Comparison of the observed ratios/slopes with those derived from emission inventories showed that while the observed SO2/NO y* ratio (1.29 ppbv/ppbv) in March was comparable (within 20%) to the inventory-derived ratio for the study region, the measured CO/NOy* slope (37 ppbv/ppbv) was about 200% larger. The observed slope of CO relative to NMHC (including ethane, propane, butanes, ethene, and ethyne) also indicated the presence of excess CO, compared to the ratios from the inventories. These results strongly suggest that emissions of CO in eastern China have been underrepresented. The findings of this study highlight the importance of characterizing trace gases and aerosols within source regions of the Asian continent. The springtime results were also compared with data previously collected at the site in 1999-2000 and with those obtained on the Transport and Chemical Evolution over the Pacific (TRACE-P) aircraft and from a coastal site in South China for the same study period. Copyright 2004 by the American Geophysical Union.