Exploring the vertical extent of breaking internal wave turbulence above deep-sea topography

A mooring equipped with 200 high-resolution temperature sensors between 6 and 404 m above the bottom was moored in 1890 m water depth above a steep, about 10° slope of Mount Josephine, NE-Atlantic. The sensors have a precision of less than 0.5 mK. They are synchronized via induction every 4 h so that the 400 m range is measured to within 0.02 s, every 1 s. Thin cables and elliptical buoyancy assured vertical mooring motions to be smaller than 0.1 m under maximum 0.2 m s⁻¹ current speeds. The local bottom slope is supercritical for semidiurnal internal tides by a factor of two. Exploring a one-month record in detail, the observations show: 1/semidiurnal tidal dominance in variations of dissipation rate ε, eddy diffusivity K_z and temperature, but no significant correlation between the records of ε and total kinetic energy, 2/a variation with time over four orders of magnitude of 100-m vertically averaged ε, 3/a local minimum in density stratification between 50 and 100 m above the bottom, 4/a gradual decrease in daily or longer averaged ε and K_z by one order of magnitude over a vertical distance of 250 m, upwards from 150 m above the bottom, 5/monthly mean values of <[ε]> = 2 ± 0.5 × 10⁻⁷ m² s⁻³, <[K_z]> = 8 ± 3 × 10⁻³ m² s⁻¹ averaged over the lower 150 m above the bottom.     

Size-resolved aerosol chemical concentrations at rural and urban sites in Central California,USA

Aerosol size distributions were measured with Micro Orifice Uniform Deposit Impactor (MOUDI) cascade impactors at the rural Angiola and urban Fresno Supersites in California's San Joaquin Valley during the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) winter campaign from December 15, 2000 to February 3, 2001. PM_2.5 filter samples were collected concurrently at both sites with Sequential Filter Samplers (SFS). MOUDI nitrate (NO₃⁻) concentrations reached 66 μg/m³ on January 6, 2001 during the 1000–1600 PST (GMT-8) period. Pair-wise comparisons between PM_2.5 MOUDI and SFS concentrations revealed high correlations at the Angiola site (r > 0.93) but more variability (r < 0.85) at the Fresno site for NO₃⁻, sulfate (SO₄⁼), and ammonium (NH₄⁺). Correlations were higher at Fresno (r > 0.87) than at Angiola (r < 0.7) for organic carbon (OC), elemental carbon (EC), and total carbon (TC). NO₃⁻ and SO₄⁼ size distributions in Fresno were multi-modal and wider than the uni-modal distributions observed at Angiola. Geometric mean diameters (GMD) were smaller for OC and EC than for NO₃⁻ and SO₄⁼ at both sites. OC and EC were more concentrated on the lowest MOUDI stage (0.056 µm) at Angiola than at Fresno. The NO₃⁻ GMD increased from 0.97 to 1.02 µm as the NO₃⁻ concentration at Angiola increased from 43 to 66 µg m^− 3 during a PM_2.5 episode from January 4–7, 2001. There was a direct relationship between GMD and NO₃⁻ and SO₄⁼ concentrations at Angiola but no such relationships for OC or EC. This demonstrates that secondary aerosol formation increases both concentration and particle size for the rural California environment.     

The origin of sub-surface source waters define the sea–air flux of methane in the Mauritanian Upwelling,NW Africa

Concentrations and flux densities of methane were determined during a Lagrangian study of an advective filament in the permanent upwelling region off western Mauritania. Newly upwelled waters were dominated by the presence of North Atlantic Central Water and surface CH₄ concentrations of 2.2 ± 0.3 nmol L⁻¹ were largely in equilibrium with atmospheric values, with surface saturations of 101.7 ± 14%. As the upwelling filament aged and was advected offshore, CH₄ enriched South Atlantic Central Water from intermediate depths of 100–350 m was entrained into the surface mixed layer of the filament following intense mixing associated with the shelf break. Surface saturations increased to 198.9 ± 15% and flux densities increased from a mean value over the shelf of 2.0 ± 1.1 μmol m⁻² d⁻¹ to a maximum of 22.6 μmol m⁻² d⁻¹. Annual CH₄ emissions for this persistent filament were estimated at 0.77 ± 0.64 Gg which equates to a maximum of 0.35% of the global oceanic budget. This raises the known outgassing intensity of this area and highlights the importance of advecting filaments from upwelling waters as efficient vehicles for air-sea exchange.     

Supply of carbon sequestration and biodiversity services from Australia's agricultural land under global change

Global agroecosystems can contribute to both climate change mitigation and biodiversity conservation, and market mechanisms provide a highly prospective means of achieving these outcomes. However, the ability of markets to motivate the supply of carbon sequestration and biodiversity services from agricultural land is uncertain, especially given the future changes in environmental, economic, and social drivers. We quantified the potential supply of these services from the intensive agricultural land of Australia from 2013 to 2050 under four global outlooks in response to a carbon price and biodiversity payment scheme. Each global outlook specified emissions pathways, climate, food demand, energy price, and carbon price modeled using the Global Integrated Assessment Model (GIAM). Using a simplified version of the Land Use Trade-Offs (LUTO) model, economic returns to agriculture, carbon plantings, and environmental plantings were calculated each year. The supply of carbon sequestration and biodiversity services was then quantified given potential land use change under each global outlook, and the sensitivity of the results to key parameters was assessed. We found that carbon supply curves were similar across global outlooks. Sharp increases in carbon sequestration supply occurred at carbon prices exceeding 50 $ tCO₂⁻¹ in 2015 and exceeding 65 $ tCO₂⁻¹ in 2050. Based on GIAM-modeled carbon prices, little carbon sequestration was expected at 2015 under any global outlook. However, at 2050 expected carbon supply under each outlook differed markedly, ranging from 0 to 189 MtCO₂ yr⁻¹. Biodiversity services of 3.32% of the maximum may be achieved in 2050 for a 1 $B investment under median scenario settings. We conclude that a carbon market can motivate supply of substantial carbon sequestration but only modest amounts of biodiversity services from agricultural land. A complementary biodiversity payment can synergistically increase the supply of biodiversity services but will not provide much additional carbon sequestration. The results were sensitive to global drivers, especially the carbon price, and the domestic drivers of adoption hurdle rate and agricultural productivity. The results can inform the design of an effective national policy and institutional portfolio addressing the dual objectives of climate change and biodiversity conservation that is robust to future uncertainty in both national and global drivers.     

Earth System Model FGOALS-s2: Coupling a dynamic global vegetation and terrestrial carbon model with the physical climate system model

Earth System Models （ESMs） are fundamental tools for understanding climate-carbon feedback. An ESM version of the Flexible Global Ocean-Atmosphere-Land System model （FGOALS） was recently developed within the IPCC AR5 Coupled Model Intercomparison Project Phase 5 （CMIP5） modeling framework, and we describe the development of this model through the coupling of a dynamic global vegetation and terrestrial carbon model with FGOALS-s2. The performance of the coupled model is evaluated as follows. The simulated global total terrestrial gross primary production （GPP） is 124.4 PgC yr-I and net pri- mary production （NPP） is 50.9 PgC yr-1. The entire terrestrial carbon pools contain about 2009.9 PgC, comprising 628.2 PgC and 1381.6 PgC in vegetation and soil pools, respectively. Spatially, in the tropics, the seasonal cycle of NPP and net ecosystem production （NEP） exhibits a dipole mode across the equator due to migration of the monsoon rainbelt, while the seasonal cycle is not so significant in Leaf Area Index （LAI）. In the subtropics, especially in the East Asian monsoon region, the seasonal cycle is obvious due to changes in temperature and precipitation from boreal winter to summer. Vegetation productivity in the northern mid-high latitudes is too low, possibly due to low soil moisture there. On the interannual timescale, the terrestrial ecosystem shows a strong response to ENSO. The model- simulated Nifio3.4 index and total terrestrial NEP are both characterized by a broad spectral peak in the range of 2-7 years. Further analysis indicates their correlation coefficient reaches -0.7 when NEP lags the Nifio3.4 index for about 1-2 months.     

One year measurements of aerosol optical properties over an urban coastal site: Effect on local direct radiative forcing

We present results of direct aerosol radiative forcing over a French Mediterranean coastal zone based on one year of continuous observations of aerosol optical properties during 2005–2006. Monthly-mean aerosol optical depth at 440 nm ranged between 0.1 and 0.34, with high Angstrom coefficient (α > 1.2). The single scattering albedo (at 525 nm) estimated at the surface ranged between 0.7 and 0.8, indicating significant absorption. The presence of aerosols over the Mediterranean zone during summer decreases the shortwave radiation reaching the surface by as much as 26 ± 3.9 W m^− 2, and increases the top of the atmosphere reflected radiation by as much as 5.2 ± 1.0 W m^− 2. The shortwave atmospheric absorption translates to an atmospheric heating of 2.5 to 4.6 K day^− 1. Concerted efforts are needed for investigating the possible impact of the increase in heating rate on the maintenance of heat-waves frequently occurring over this coastal region during summer time.     

Using the mean pressure gradient and NCEP/NCAR reanalysis to estimate the strength of the South Atlantic Anticyclone

A new methodology is proposed to estimate the strength of the South Atlantic Anticyclone (SAA), using the gridded sea level pressure (SLP) of the National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) Reanalysis data. The top quartile (1017.3 hPa) of the SLP data was found a reasonable criterion to delimit the SAA area. Consequently, we defined the SAA area as the quadrangle containing 80% of the observations with pressure >1017.3 hPa. In this quadrangle, an area weighted pressure gradient (AWPG) was computed for the whole area and for the north–south and west–east halves. When compared with maximum pressure, the AWPG showed a better correlation with the significant wave height (SWH) and wind speed (WS) derived from altimetry. The mean value of the AWPG was 8 × 10⁻⁴ Pa/m, with representative values of 9.1 × 10⁻⁴ Pa/m and 7.4 × 10⁻⁴ Pa/m for austral winter and summer, respectively. The phase difference between the monthly AWPG in the north and south sub-quadrangles accounts for the evolution of the spatial pattern of the anticyclone throughout a year. This quantitative approach proved to be a useful estimate of the strength of South Atlantic Anticyclone. Further improvements of this approach are discussed.     

Kinematic metrics of the Loop Current in the Gulf of Mexico from satellite altimetry

We analyzed a 20-year time series (January 1st, 1993 through December 31st, 2012) of Loop Current (LC) surface area derived from satellite altimetry in the eastern Gulf of Mexico to estimate kinematical metrics of this potent flow. On average the LC intrudes to its maximum northward position about 216 ± 126 days after the previous eddy separation; and ∼30 ± 31 days later sheds a large anticyclonic eddy. When the northern extent of the LC intrusion following the previous eddy separation is greater than 27°N, the current retreats very quickly until it sheds another eddy with the entire separation process occurring on the order of 30 days. To first order the change in areal extent of the LC during intrusion into the Gulf occurs at an average rate of 225 km² day⁻¹, which corresponds to an intrusion velocity of 1.7 cm s⁻¹ of the LC front, and adds Caribbean water to the Gulf at a rate of 2.6 ± 0.7 Sv.     

Observations and operational model simulations reveal the impact of Hurricane Matthew (2016) on the Gulf Stream and coastal sea level

In October 7–9, 2016, Hurricane Matthew moved along the southeastern coast of the U.S., causing major flooding and significant damage, even to locations farther north well away from the storm’s winds. Various observations, such as tide gauge data, cable measurements of the Florida Current (FC) transport, satellite altimeter data and high-frequency radar data, were analyzed to evaluate the impact of the storm. The data show a dramatic decline in the FC flow and increased coastal sea level along the U.S. coast. Weakening of the Gulf Stream (GS) downstream from the storm’s area contributed to high coastal sea levels farther north. Analyses of simulations of an operational hurricane-ocean coupled model reveal the disruption that the hurricane caused to the GS flow, including a decline in transport of ∼20 Sv (1 Sv = 10⁶ m³ s⁻¹). In comparison, the observed FC reached a maximum transport of ∼40 Sv before the storm on September 10 and a minimum of ∼20 Sv after the storm on October 12. The hurricane impacts both the geostrophic part of the GS and the wind-driven currents, generating inertial oscillations with velocities of up to ±1 m s⁻¹. Analysis of the observed FC transport since 1982 indicated that the magnitude of the current weakening in October 2016 was quite rare (outside 3 standard deviations from the mean). Such a large FC weakening in the past occurred more often in October and November, but is extremely rare in June-August. Similar impacts on the FC from past tropical storms and hurricanes suggest that storms may contribute to seasonal and interannual variations in the FC. The results also demonstrated the extended range of coastal impacts that remote storms can cause through their influence on ocean currents.     

Impressions of the turbulence variability in a weakly stratified,flat-bottom deep-sea ‘boundary layer’

The character of turbulent overturns in a weakly stratified deep-sea is investigated in some detail using 144 high-resolution temperature sensors at 0.7 m intervals, starting 5 m above the bottom. A 9-day, 1 Hz sampled record from the 912 m depth flat-bottom (<0.5% bottom-slope) mooring site in the central-north Alboran Sea (W-Mediterranean) demonstrates an overall conservative temperature range of only 0.05 °C, a typical mean buoyancy period as large as 3 h and a 1 Hz-profile-vertically-averaged turbulence dissipation rate maximum of only 10⁻⁸ m² s⁻³. Nonetheless, this ‘boundary layer’ varies in height between <6 and >104 m above the bottom and is thus not homogeneous throughout; the temperature variations are seldom quiescent and are generally turbulent in appearance, well exceeding noise levels. The turbulence character is associated with small-scale internal waves; examples are found of both shear- and convection-driven turbulence; particular association, although not phase-locked, is found between turbulence variations and tidal rather than with inertial motions; the mean buoyancy frequency of a few times the inertial frequency implies the importance of ‘slantwise convection’ in the direction of the earth rotational vector rather than in the direction of gravity. Such convection is observed both in near-homogeneous and weakly stratified form.     

Water on an urban planet: Urbanization and the reach of urban water infrastructure

Urban growth is increasing the demand for freshwater resources, yet surprisingly the water sources of the world's large cities have never been globally assessed, hampering efforts to assess the distribution and causes of urban water stress. We conducted the first global survey of the large cities’ water sources, and show that previous global hydrologic models that ignored urban water infrastructure significantly overestimated urban water stress. Large cities obtain 78 ± 3% of their water from surface sources, some of which are far away: cumulatively, large cities moved 504 billion liters a day (184 km³ yr⁻¹) a distance of 27,000 ± 3800 km, and the upstream contributing area of urban water sources is 41% of the global land surface. Despite this infrastructure, one in four cities, containing $4.8 ± 0.7 trillion in economic activity, remain water stressed due to geographical and financial limitations. The strategic management of these cities’ water sources is therefore important for the future of the global economy.     

Analysis of rainfall characteristics of the Madden–Julian oscillation using TRMM satellite data

Rainfall characteristics of the Madden–Julian oscillation (MJO) are analyzed primarily using tropical rainfall measuring mission (TRMM) precipitation radar (PR), TRMM microwave imager (TMI) and lighting imaging sensor (LIS) data. Latent heating structure is also examined using latent heating data estimated with the spectral latent heating (SLH) algorithm.The zonal structure, time evolution, and characteristic stages of the MJO precipitation system are described. Stratiform rain fraction increases with the cloud activity, and the amplitude of stratiform rain variation associated with the MJO is larger than that of convective rain by a factor of 1.7. Maximum peaks of both convective rain and stratiform rain precede the minimum peak of the outgoing longwave radiation (OLR) anomaly which is often used as a proxy for the MJO convection. Stratiform rain remains longer than convective rain until ∼4000 km behind the peak of the mature phase. The stratiform rain contribution results in the top-heavy heating profile of the MJO.Associated with the MJO, there are tri-pole convective rain top heights (RTH) at 10–11, ∼7 and ∼3 km, corresponding to the dominance of afternoon showers, organized systems, and shallow convections, respectively. The stratiform rain is basically organized with convective rain, having similar but slightly lower RTH and slightly lags the convective rain maximum. It is notable that relatively moderate (∼7 km) RTH is dominant in the mature phase of the MJO, while very tall rainfall with RTH over 10 km and lightning frequency increase in the suppressed phase. The rain-yield-per flash (RPF) varies about 20–100% of the mean value of ∼2–10 × 10⁹ kg fl⁻¹ over the tropical warm ocean and that of ∼2–5 × 10⁹ kg fl⁻¹ over the equatorial Islands, between the convectively suppressed phase and the active phase of MJO, in the manner that RPF is smaller in the suppressed phase and larger in the active phase.     

Carbonaceous materials in size-segregated atmospheric aerosols from urban and coastal-rural areas at the Western European Coast

A high-volume cascade impactor, equipped with a PM10 inlet, was used to collect size-segregated aerosol samples during the summer of 2004 at two Portuguese locations: a coastal-rural area (Moitinhos) and an urban area (Oporto). Concentrations of airborne particulate matter (PM), total carbon (TC), organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were determined for the following particle size ranges: < 0.49, 0.49–0.95, 0.95–3.0, and 3.0–10 µm. The total PM mass concentrations at the urban and coastal-rural sites ranged from 22.8 to 79.6 μg m^− 3 and 19.9 to 28.2 μg m^− 3, respectively, and more than 56% of the total aerosol mass was found in the fractions below 3.0 μm. At both locations the highest concentrations of OC and EC were found in the submicrometer size range. The regional variability for the OC and EC concentrations, with the highest concentrations being found in the urban area, was related to the contribution of local primary sources (mostly traffic emissions). It was also verified an enrichment of the small size particles in WSOC, representing on average 37.3(± 12.4)% and 59.7(± 18.0)% of OC in the very fine aerosol at the coastal-rural and urban areas, respectively. The amount of secondary OC calculated by the minimum OC/EC ratio method indicates that secondary organic aerosol formation was important throughout the study at both sites. The obtained results suggest that long-range transport and favourable summer conditions for photochemical oxidation are key factors determining secondary OC formation in the coastal-rural and urban areas. The ultraviolet absorption properties of the chromophoric constituents of the WSOC fractions were also different among the different particle size ranges and also between the two sampling locations, thus suggesting the strong impact of the diverse emission sources into the composition of the size-segregated organic aerosol.     

Nitrate in groundwater of China: Sources and driving forces

Identifying the sources of reactive nitrogen (N) and quantifying their contributions to groundwater nitrate concentrations are critical to understanding the dynamics of groundwater nitrate contamination. Here we assessed groundwater nitrate contamination in China using literature analysis and N balance calculation in coupled human and natural systems. The source appointment via N balance was well validated by field data via literature analysis. Nitrate was detected in 96% of groundwater samples based on a common detection threshold of 0.2 mg N L^?1, and 28% of groundwater samples exceeded WHO's maximum contaminant level (10 mg N L^?1). Groundwater nitrate concentrations were the highest beneath industrial land (median: 34.6 mg N L^?1), followed by urban land (10.2 mg N L^?1), cropland (4.8 mg N L^?1), and rural human settlement (4.0 mg N L^?1), with the lowest found beneath natural land (0.8 mg N L^?1). During the period 1980–2008, total reactive N leakage to groundwater increased about 1.5 times, from 2.0 to 5.0 Tg N year^?1, in China. Despite that the contribution of cropland to the total amount of reactive N leakage to groundwater was reduced from 50 to 40% during the past three decades, cropland still was the single largest source, while the contribution from landfill rapidly increased from 10 to 34%. High reactive N leakage mainly occurred in relatively developed agricultural or urbanized regions with a large population. The amount of reactive N leakage to groundwater was mainly driven by anthropogenic factors (population, gross domestic product, urbanization rate and land use type). We constructed a high resolution map of reactive N source appointment and this could be the basis for future modeling of groundwater nitrate dynamics and for policy development on mitigation of groundwater contamination.     

Globalisation of water resources: international virtual water flows in relation to crop trade

The water that is used in the production process of a commodity is called the ‘virtual water’ contained in the commodity. International trade of commodities brings along international flows of virtual water. The objective of this paper is to quantify the volumes of virtual water flows between nations in the period 1995–1999 insofar related to international crop trade and to analyse national virtual water balances in relation to national water needs and water availability. The basic approach is to multiply international crop trade flows (ton/yr) by their associated virtual water content (m³ ton⁻¹). The calculations show that the global volume of crop-related international virtual water flows between nations was 695 Gm³ yr⁻¹ in average over the period 1995–1999. For comparison: the total water use by crops in the world has been estimated at 5400 Gm³ yr⁻¹. This means that 13% of the water used for crop production in the world is not used for domestic consumption but for export (in virtual form). This is a conservative estimate because only a limited number of crops––although the most important ones––have been taken into account and because crop products (such as cotton clothes) have been excluded from the study. The countries with the largest net virtual water export are United States, Canada, Thailand, Argentina and India. The largest net import appears to be in Japan, the Netherlands, the Republic of Korea, China and Indonesia.     

Oil palm expansion in Cameroon: Insights into sustainability opportunities and challenges in Africa

Oil palm production expanded 1.2 million hectares in sub-Saharan Africa since 1990, with expansion accelerating in several heavily forested countries since 2000. Despite a narrative of expansion driven by multinational corporations, we provide evidence of a dynamic non-industrial oil palm production sector linked to a burgeoning informal milling enterprise. Surveys were conducted with oil palm farmers in Cameroon (n = 546), the third largest palm oil producer on the continent with the greatest amount of deforestation due to recent expansion, to determine who is expanding into forest. Seventy-three percent of survey respondents reported clearing forest, the magnitude of which was explained by differences in milling strategies and supply chain integration. Large-scale, non-industrial producers played a disproportionate role in deforestation, many of which were engaged in informal supply chains through the use of non-industrial mills. Farms associated with more clearing tended to use high-yielding seedlings. Even the highest yielding farms, however, averaged only 7.7 tons fresh fruit bunches (FFBs) ha⁻¹ yr⁻¹, well below the potential 20 tons FFBs ha⁻¹ yr⁻¹ yield for Cameroon. We also found a strong relationship between deforestation and land claims. Most farms claimed ownership of their land, although only 5% had official land titles. Conservation challenges in the region arise from land tenure laws that incentivize forest clearing. This study sheds light on the role of informal supply chains in deforestation and highlights the need for strict implementation and enforcement of land use zoning policies.     

Distribution of CO2 parameters in the Western Tropical Atlantic Ocean

The variability of sea surface Total Alkalinity (TA) and sea surface Total Inorganic Carbon (C_T) is examined using all available data in the western tropical Atlantic (WTA: 20°S-20°N, 60°W-20°W). Lowest TA and C_T are observed for the region located between 0°N-15°N/60°W-50°W and are explained by the influence of the Amazon plume during boreal summer. In the southern part of the area, 20°S-10°S/40°W-60°W, the highest values of TA and C_T are linked to the CO₂–rich waters due to the equatorial upwelling, which are transported by the South Equatorial Current (SEC) flowing from the African coast to the Brazilian shore. An increase of C_T of 0.9 ± 0.3 μmol kg⁻¹yr⁻¹ has been observed in the SEC region and is consistent with previous published estimates. A revised C_T-Sea Surface Salinity (SSS) relationship is proposed for the WTA to take into account the variability of C_T at low salinities. This new C_T-SSS relationship together with a published TA-SSS relationship allow to calculate pCO₂ values that compare well with observed pCO₂ (R² = 0.90).     

Past and future carbon sequestration benefits of China’s grain for green program

Carbon sequestration through ecological restoration programs is an increasingly important option to reduce the rise of atmospheric carbon dioxide concentration. China’s Grain for Green Program (GGP) is likely the largest centrally organized land-use change program in human history and yet its carbon sequestration benefit has yet to be systematically assessed. Here we used seven empirical/statistical equations of forest biomass carbon sequestration and five soil carbon change models to estimate the total and decadal carbon sequestration potentials of the GGP during 1999–2050, including changes in four carbon pools: aboveground biomass, roots, forest floor and soil organic carbon. The results showed that the total carbon stock in the GGP-affected areas was 682 Tg C in 2010 and the accumulative carbon sink estimates induced by the GGP would be 1697, 2635, 3438 and 4115 Tg C for 2020, 2030, 2040 and 2050, respectively. Overall, the carbon sequestration capacity of the GGP can offset about 3%–5% of China’s annual carbon emissions (calculated using 2010 emissions) and about 1% of the global carbon emissions. Afforestation by the GGP contributed about 25% of biomass carbon sinks in global carbon sequestration in 2000–2010. The results suggest that large-scale ecological restoration programs such as afforestation and reforestation could help to enhance global carbon sinks, which may shed new light on the carbon sequestration benefits of such programs in China and also in other regions.     

Below-cloud rain scavenging of atmospheric aerosols for aerosol deposition models

Below-cloud aerosol scavenging is generally estimated from field measurements using advanced instruments that measure changes in aerosol distributions with respect to rainfall. In this study, we discuss various scavenging mechanisms and scavenging coefficients from past laboratory and field measurements. Scavenging coefficients derived from field measurements (representing natural aerosols scavenging) are two orders higher than that of theoretical ones for smaller particles (D_p < 2 μm). Measured size-resolved scavenging coefficients can be served as a better option to the default scavenging coefficient (e.g. a constant of 10^?4 s^?1 for all size of aerosols, as used in the CALPUFF model) for representing below-cloud aerosol scavenging. We propose scavenging correction parameter (C_R) as an exponential function of size-resolved scavenging coefficients, winds and width in the downwind of the source–receptor system. For a wind speed of 3 m s^?1, C_R decrease with the width in the downwind for particles of diameters D_p < 0.1 μm but C_R does not vary much for particles in the accumulation mode (0.1 < D_p < 2 μm). For a typical urban aerosol distribution, assuming 3 m s^?1 air-flow in the source–receptor system, 10 km downwind width, 2.84 mm h^?1 of rainfall and using aerosol size dependent scavenging coefficients in the C_R, scavenging of aerosols is found to be 16% in number and 24% in volume of total aerosols. Using the default scavenging coefficient (10^?4 s^?1) in the CALPUFF model, it is found to be 64% in both number and volume of total aerosols.     

Evidence of high PM2.5 strong acidity in ammonia-rich atmosphere of Guangzhou,China: Transition in pathways of ambient ammonia to form aerosol ammonium at [NH4+]/[SO42–] = 1.5

In this study, 24-h PM_2.5 samples were collected using Harvard Honeycomb denuder/filter-pack system during different seasons in 2006 and 2007 at an urban site in Guangzhou, China. The particles collected in this study were generally acidic (average strong acidity ([H⁺]) ~ 70 nmol m^? 3). Interestingly, aerosol sulfate was not fully neutralized in the ammonia-rich atmosphere (NH₃ ~ 30 ppb) and even when NH₄⁺]/[SO₄^2?] was larger than 2. Consequently, strong acidity ([H⁺]) as high as 170 nmol m^? 3 was observed in these samples. The kinetic rate of neutralization of acidity (acidic sulfate) by ambient ammonia was significantly higher than the rate of formation of ammonium nitrate involving HNO₃ and NH₃ for [NH₄⁺]/[SO₄^2?] ≤ 1.5 and much lower for NH₄⁺]/[SO₄^2?] > 1.5. Therefore, higher nitrate principally formed via homogeneous gas phase reactions involving ammonia and nitric acid were observed for [NH₄⁺]/[SO₄^2?] > 1.5. However, little nitrate, probably formed via heterogeneous processes e.g. reaction of HNO₃ with sea salt or crustal species, was observed for [NH₄⁺]/[SO₄^2?] ≤ 1.5. These demonstrate a clear transition in the pathways of ambient ammonia to form aerosol ammonium at [NH₄⁺]/[SO₄^2?] = 1.5 and evidently explain the observed high acidity due to the unneutralized sulfate in the ammonium-rich aerosol (NH₄⁺]/[SO₄^2?] > 1.5). In fact, the measured acidity was almost similar to the excess acid defined as the acid that remains at [NH₄⁺]/[SO₄^2?] = 1.5 due to the un-neutralized fraction of sulfate ([H⁺] = 0.5[SO₄^2?]). The presence of high excess acid and ammonium nitrate significantly lowered the deliquescence relative humidity of ammonium sulfate (from 80% to 40%) in the ammonium-rich samples.