Long-term observations of cloud condensation nuclei over the Amazon rain forest – Part 2 : Variability and characteristics of biomass burning , long-range transport , and pristine rain forest aerosols

Size-resolved measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations and hygroscopicity were conducted over a full seasonal cycle at the remote Amazon Tall Tower Observatory (ATTO, March 2014–February 2015). In a preceding companion paper, we presented annually and seasonally averaged data and parametrizations (Part 1; Pöhlker et al., 2016a). In the present study (Part 2), we analyze key features and implications of aerosol and CCN properties for the following characteristic atmospheric conditions: – Empirically pristine rain forest (PR) conditions, where no influence of pollution was detectable, as observed during parts of the wet season from March to May. The PR episodes are characterized by a bimodal aerosol size distribution (strong Aitken mode with DAit≈ 70 nm and NAit≈ 160 cm−3, weak accumulation mode with Dacc≈ 160 nm and Nacc ≈ 90 cm−3), a chemical composition dominated by organic compounds, and relatively low particle hygroscopicity (κAit ≈ 0.12, κacc ≈ 0.18). – Long-range-transport (LRT) events, which frequently bring Saharan dust, African biomass smoke, and sea spray aerosols into the Amazon Basin, mostly during February to April. The LRT episodes are characterized by a dominant accumulation mode (DAit≈ 80 nm, NAit≈ 120 cm−3 vs.Dacc≈ 180 nm,Nacc≈ 310 cm−3), an increased abundance of dust and salt, and relatively high hygroscopicity (κAit ≈ 0.18, κacc≈ 0.35). The coarse mode is also significantly enhanced during these events. – Biomass burning (BB) conditions characteristic for the Amazonian dry season from August to November. The BB episodes show a very strong accumulation mode (DAit≈ 70 nm, NAit≈ 140 cm−3 vs. Dacc≈ 170 nm, Nacc≈ 3400 cm−3), very high organic mass fractions (∼ 90 %), and correspondingly low hygroscopicity (κAit ≈ 0.14, κacc≈ 0.17). – Mixed-pollution (MPOL) conditions with a superposition of African and Amazonian aerosol emissions during the dry season. During the MPOL episode presented here as a case study, we observed African aerosols with a broad monomodal distribution (D≈ 130 nm, NCN,10≈ 1300 cm−3), with high sulfate mass fractions (∼ 20 %) from volcanic sources and correspondingly high hygroscopicity (κ< 100 nm ≈ 0.14, κ> 100 nm ≈ 0.22), which were periodically mixed with fresh smoke from nearby fires (D≈ 110 nm, NCN,10≈ 2800 cm−3) with an organicdominated composition and sharply decreased hygroscopicity (κ< 150 nm ≈ 0.10, κ> 150 nm ≈ 0.20). Insights into the aerosol mixing state are provided by particle hygroscopicity (κ) distribution plots, which indicate largely internal mixing for the PR aerosols (narrow κ distribution) and more external mixing for the BB, LRT, and MPOL aerosols (broad κ distributions). The CCN spectra (CCN concentration plotted against water vapor supersaturation) obtained for the different case studies indicate distinctly different regimes of cloud formation and microphysics depending on aerosol properties and meteorological conditions. The measurement results suggest that CCN activation and droplet formation in convective clouds are mostly aerosol-limited under PR and LRT conditions and updraft-limited under BB and MPOL conditions. Normalized CCN efficiency spectra (CCN divided by aerosol number concentration plotted against water vapor supersaturation) and corresponding parameterizations (Gaussian error function fits) provide a basis for further analysis and model studies of aerosol–cloud interactions in the Amazon.

Abstract. Size-resolved measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations and hygroscopicity were conducted over a full seasonal cycle at the remote Amazon Tall Tower Observatory (ATTO, March 2014-February 2015. In a preceding companion paper, we presented annually and seasonally averaged data and parametrizations (Part 1; Pöhlker et al., 2016a). In the present study (Part 2), we analyze key features and implications of aerosol and CCN properties for the following characteristic atmospheric conditions: -Empirically pristine rain forest (PR) conditions, where no influence of pollution was detectable, as observed during parts of the wet season from March to May. The PR episodes are characterized by a bimodal aerosol size distribution (strong Aitken mode with D Ait ≈ 70 nm and N Ait ≈ 160 cm −3 , weak accumulation mode with D acc ≈ 160 nm and N acc ≈ 90 cm −3 ), a chemical composition dominated by organic compounds, and relatively low particle hygroscopicity (κ Ait ≈ 0.12, κ acc ≈ 0.18).
-Long-range-transport (LRT) events, which frequently bring Saharan dust, African biomass smoke, and sea spray aerosols into the Amazon Basin, mostly during February to April. The LRT episodes are characterized by a dominant accumulation mode (D Ait ≈ 80 nm, N Ait ≈ 120 cm −3 vs. D acc ≈ 180 nm, N acc ≈ 310 cm −3 ), an increased abundance of dust and salt, and relatively high hygroscopicity (κ Ait ≈ 0.18, κ acc ≈ 0.35). The coarse mode is also significantly enhanced during these events.
Insights into the aerosol mixing state are provided by particle hygroscopicity (κ) distribution plots, which indicate largely internal mixing for the PR aerosols (narrow κ distribution) and more external mixing for the BB, LRT, and MPOL aerosols (broad κ distributions).
The CCN spectra (CCN concentration plotted against water vapor supersaturation) obtained for the different case studies indicate distinctly different regimes of cloud formation and microphysics depending on aerosol properties and meteorological conditions. The measurement results suggest that CCN activation and droplet formation in convective clouds are mostly aerosol-limited under PR and LRT conditions and updraft-limited under BB and MPOL conditions. Normalized CCN efficiency spectra (CCN divided by aerosol number concentration plotted against water vapor supersaturation) and corresponding parameterizations (Gaussian error function fits) provide a basis for further analysis and model studies of aerosol-cloud interactions in the Amazon.

Introduction
Clouds are a key factor in the Earth's atmosphere and climate system (Bony et al., 2015). Thus, sound scientific knowledge on the life cycle and highly dynamic properties of clouds is of significant importance for our understanding of atmospheric cycling and climate change (Seinfeld et al., 2016). A number of recent overview studies summarize the various facets of aerosol-cloud-precipitation-climate interactions in a detailed and comprehensive way (e.g., Andreae and Rosenfeld, 2008;Tao et al., 2012;Rosenfeld et al., 2014).
The Amazon Basin and its unique rain forest ecosystem are fundamentally shaped by the intense and large-scale (re)circulation of water between biosphere and atmosphere. Accordingly, the life cycle of shallow and deep convective clouds in the Amazon has been subject of numerous previous studies (e.g., Andreae et al., 2004;Freud et al., 2008;Rosenfeld et al., 2016;Wendisch et al., 2016;Braga et al., 2017). In particular, the extent of anthropogenic influence on the cloud life cycle through continuous land use change and combustion-related aerosol emissions has been actively debated (e.g., Roberts et al., 2003;Davidson et al., 2012;Goncalves et al., 2015). It is well established that the properties and dynamics of clouds can be fundamentally altered by changing cloud condensation nuclei (CCN) regimes, which are a fraction of the total (tropospheric) aerosol population (e.g., Rosenfeld et al., 2008;Reutter et al., 2009).
To explore essential biogeochemical processes, such as aerosol-cloud interactions, in the Amazon rain forest, the Amazon Tall Tower Observatory (ATTO) was established in 2010/11 (for details see Andreae et al., 2015). The central Amazon Basin is characterized by a pronounced seasonality in atmospheric composition in response to the north-south oscillation of the Intertropical Convergence Zone (ITCZ). During the wet season, the ATTO site receives comparatively clear air masses of marine origin from the northeast that travel over mostly untouched rain forest areas, whereas during the dry season strongly polluted air masses are advected from the southeast, originating from numerous fires in the Amazon's arc of deforestation (for details see C. . Detailed information on characteristic differences in the atmospheric state and processes for the contrasting wet-vs. dry-season conditions in the ATTO region can be found in a number of recent studies (e.g., Nölscher et al., 2016;Pöhlker et al., 2016;Moran-Zuloaga et al., 2017;Saturno et al., 2017a;Yañez-Serrano et al., 2018).
In terms of microphysical processes in cloud formation and development, the number concentration of CCN, N CCN (S), and the peak water vapor supersaturation, S, at the cloud base play a key role. Here, S is predominantly determined by the updraft velocity, w b , of the adiabatically rising air parcel at the cloud base. The relevant peak S levels in the Amazon are assumed to range from ∼ 0.1 to ∼ 1.0 % (e.g., Andreae, 2009;Reutter et al., 2009;Pöschl et al., 2010;Pöhlker et al., 2012;Farmer et al., 2015;Pöhlker et al., 2016). Moreover, a recent study suggests that substantially higher S ( 1 %) can also be reached in deep convective clouds under certain conditions (Fan et al., 2018). However, a systematic and quantitative assessment of relevant peak S distributions in the Amazonian atmosphere is still lacking (see discussion in Sect. 3.9). Depending on N CCN (S) and S, a certain number of cloud droplets at the cloud base, N db , are formed . In the Amazon Basin, N db ranges from a few hundred droplets per cubic centimeter for clean conditions to 1000 and 2000 cm −3 for polluted conditions Rosenfeld et al., 2016;Braga et al., 2017). Upon cloud development and rising air masses, the initial droplets grow by condensation of water vapor, which can be observed as changes in the cloud drop size distribution (DSD). Thus, the DSD is a function of thermodynamic parameters (i.e., the updraft velocity, w b ), aerosol conditions (i.e., N CCN (S)), and the cloud evolution (i.e., the cloud depth, H ). Important bulk DSD properties are, in particular, the droplet number concentration, N d , and the effective droplet radius, r e . For r e > 11 µm, the probability of droplet collision and coalescence processes increases to significant levels, and warm rain formation is initiated (Cecchini et al., 2017a).
A detailed analysis of the properties and variability of the Amazonian CCN population is a prerequisite for the understanding of cloud cycling in this region. However, the CCN data from the basin is still sparse. Therefore, we conducted a systematic characterization of the trends and properties of the central Amazonian CCN population at the ATTO site. The first half of this study has been published recently as Part 1 . The present paper represents Part 2 and focuses on the variability and properties of periods and conditions that are characteristic for the Amazonian atmosphere.

Brief summary of the Part 1 companion paper
The Part 1 paper  focuses on the multimonth variability in the Amazonian CCN population by presenting data from a full seasonal cycle. In particular, it presents annual averages of the key CCN parameters, a detailed analysis of the specific seasonal as well as diurnal cycles, and a systematic analysis of different CCN parametrization schemes to represent the Amazonian CCN cycling in modeling studies.
The major findings of Part 1 can be summarized as follows: (i) the CCN population in the central Amazon is predominantly defined by the overall aerosol concentration as well as the shape of the characteristic bimodal aerosol size distribution. Accordingly, a key property that has to be taken into account for the interpretation of the CCN results is the relative proportion of the Aitken and accumulation modes (mode maxima at D Ait ≈ 70 and D Acc ≈ 150 nm). (ii) The hygroscopicity parameters, κ(S, D a ) with D a as the midpoint activation diameter, of the two modes were found to be remarkably stable for most of the observation period (κ Ait = 0.14 ± 0.03 vs. κ Acc = 0.22 ± 0.05), with only weak seasonal and no diurnal variability. Accordingly, we concluded in Part 1 that the shape of the aerosol size distribution is the predominant factor, whereas κ(S, D a ) is only of secondary importance for the variability in the Amazonian CCN population, in agreement with previous studies (see references in Pöhlker et al., 2016). (iii) Furthermore, Part 1 summarizes the CCN key parameters that allow for efficient modeling of the Amazonian CCN population. The prediction of CCN concentrations is particularly reliable when time series of total aerosol concentration and/or the aerosol size distribution are available.
We emphasized CCN efficiency spectra, which can be regarded as CCN signatures for a particular aerosol population, by describing their behavior for the atmospherically relevant S range. Here, a rather simple analytical expression (i.e., single-or double-error-function fits) suffices to represent the essence of the CCN-relevant properties of an aerosol population, which includes the characteristic shape of the aerosol size distribution and the κ(S, D a ) size dependence. Furthermore, the CCN efficiency spectra are independent of the total aerosol number concentration (in contrast to CCN spectra) and, thus, can be flexibly scaled to the concentration range of interest to obtain CCN concentrations at a certain S level. Finally, and beyond their potential use in models as CCN parametrization, the shape of the CCN efficiency spectra is very instructive for visualization of the specific behavior of contrasting aerosol population in cloud formation. This aspect will be one focal point of the present study.

Aims and scope of this study
To complete the analysis started in Part 1, this paper analyzes the CCN variability at the original time resolution (∼ 4.5 h), which is sufficient to resolve its short-term variability in relation to air mass changes as well as aerosol emission and transformation processes. In the present work, we will zoom into specific periods of the 1-year CCN data set in two steps: first, we discuss the aerosol and CCN variability for two contrasting 2-month periods that characterize the pollution minimum and maximum in relation to complementary trace gas and aerosol parameters. Second, we analyze the following four case studies, which represent characteristic events and conditions in the central Amazon region: -During certain wet-season episodes, when no tracers of pollution aerosols are detectable anymore, the aerosol population can be regarded as empirically not distinguishable from pristine, i.e., completely unpolluted rain forest conditions. This empirically pristine state of the rain forest (PR) aerosol prevails during 10 to 40 days per year (depending on PR definition; see Sect. 2.7).
-Long-range-transport (LRT) aerosol advection during the wet season brings Saharan dust, African biomass burning smoke, and marine aerosol particles from the transatlantic passage. The LRT case study represents conditions that prevail between 50 and 60 days per year (see Moran-Zuloaga et al., 2017).
-Biomass burning (BB) smoke from man-made forest fires in the various deforestation hot spots in the basin influences the atmospheric state at ATTO almost permanently during the dry season and for extended episodes during the transition periods (> 100 days per year) (Saturno et al., 2017a). The BB case study in this work analyzes large deforestation fires in the southeastern basin, whose smoke reached ATTO after a few days of atmospheric processing. Accordingly, the BB case study characterizes the typical conditions of aged smoke influencing the atmospheric state at ATTO.
-Mixed pollution (MPOL) from African LRT and local/regional fires represents a frequent aerosol scenario at ATTO (Saturno et al., 2017a). The advected African aerosols mainly comprise biomass and fossil fuel combustions emissions, although the exact composition of these dry-season LRT plumes is still poorly analyzed. The MPOL case study focuses on a period when African volcanogenic aerosols were advected to ATTO -an event that has been well documented in Saturno et al. (2017b). We selected this episode since the microphysical properties of the volcanogenic aerosol are characteristic enough to discriminate them from the local/regional smoke emissions. Accordingly, the alternating pattern of LRT vs. local/regional pollution can be clearly resolved for the MPOL period. However, note that volcanogenic plumes are comparatively rare events, whereas African combustion emissions, which are much harder to discriminate from the local/regional emissions, are a more common scenario.
Accordingly, the MPOL case study is an example of a complex aerosol mixture due to alternating African vs. local/region influences during the dry season.
In summary, the overall purpose of this study is to link the measured CCN abundance and properties with the characteristic emissions and transformation processes that govern the Amazonian aerosol population. With the CCN parametrization strategies developed in Part 1, we provide a basis for effective CCN prediction under characteristic aerosol and CCN conditions in the Amazon Basin.
2 Experimental section 2.1 Aerosol and trace gas measurements at the ATTO site The present study is mostly based on in situ measurements at the remote ATTO site, which has been described in detail by Andreae et al. (2015). Further relevant information regarding the site, the measurement period, and the aerosol and trace gas instrumentation can be found in the Part 1 paper by Pöhlker et al. (2016). The time frame of the present analysis, including the four in-depth case studies, overlapped with the two intensive observation periods (IOPs) of the international Green Ocean Amazon 2014/5 (GoAmazon2014/5) campaign (Martin et al., 2016a, b). Specific details on the measurements of equivalent black carbon (BC e ) mass concentrations, M BC e , with the Multiangle Absorption Photometer (MAAP) can be found in Saturno et al. (2017a, c). Specific details on the measurements of the mole fraction of carbon monoxide (CO), c CO , with a G1302 analyzer (Picarro Inc. Santa Clara, CA, USA) can be found in Winderlich et al. (2010). Details on the Aerosol Chemical Speciation Monitor (ACSM, Aerodyne Research Inc., Billerica, MA, USA) measurements -which provide online information on the mass concentrations, M species , of organics (OA), sulfate (SO 2− 4 ), nitrate (NO − 3 ), ammonium (NH + 4 ), and chloride (Cl − ) -can be found in Ng et al. (2011). A detailed description of the long-term operation of the ACSM at the ATTO site can be found in Carbone et al. (2017). For the selected case study and seasonal time frames, we calculated the mean values of M species as well as corresponding mass fractions, f species , according to Furthermore, predicted hygroscopicity parameters, κ p , were calculated based on the ACSM and MAAP results according to the following procedure adapted from Gunthe et al. (2009), Rose et al. (2011), andPöhlker et al. (2016): with f inorg including SO 2− 4 , NO − 3 , NH + 4 , and Cl − . Note that M NH 4 ranged below its detection limit (i.e., 0.28 µg m −3 , for  Table 3, which is discussed later in this study). For these periods with questionable results, M NH 4 was omitted in the calculation of the mass fractions, which has to be kept in mind in the interpretation of the results. M Cl and M BC e were also below detection limits for certain conditions. Accordingly, κ p was calculated without M NH 4 , M Cl-, and/or M BC e . The nominal size range of the ACSM spans from 75 to 650 nm, and the measurements are conducted size-integrated. Accordingly, the ACSM results tend to be dominated by larger particles with relatively high masses, which makes the M species results mostly representative for the accumulation mode composition. Accordingly, the calculated κ p was compared to the hygroscopicity parameter for the lowest measured S level, κ(0.11 %), corresponding to the largest measured critical diameter (D a ≈ 170 nm).

CCN measurements and data analysis
A detailed description of the operation of the CCN counter (CCNC) and the subsequent data analysis can be found in the companion paper , which is the basis for the present study. Briefly, size-resolved CCN measurements were conducted using a continuous-flow streamwise thermal-gradient CCN counter (model CCN-100, DMT, Longmont, CO, USA) in combination with a differential mobility analyzer (DMA, model M, Grimm Aerosol Technik, Ainring, Germany) and a condensation particle counter (Grimm Aerosol Technik). The DMA-selected size range spans from 20 to 245 nm. The analyzed supersaturation range spans from 0.11 to 1.10 %. A complete measurement cycle with scanning of all particle diameters and supersaturations took ∼ 4.5 h. For further CCN-relevant information, we refer the reader to Rose et al. (2008) and Krüger et al. (2014). The CCN efficiency spectra parameterization as introduced in Part 1 plays a key role in the present paper. Note that we slightly revised and improved the fitting procedure from the Part 1 companion paper. The main change implies that the fits are now forced through zero, which is physically more plausible and makes the single-error-function (erf) fit parametrization more applicable for modeling studies. The erf fit (mode = 1) is represented by the following function: with a 1 as a prefactor; S 1 as the supersaturation, at which half of the maximum activated fraction (MAF) of the aerosol particles acts as CCN (e.g., 50 % for a 1 = 1); and w 1 as the width of the erf fit. To simplify the fitting procedure, a 1 = 1 was assumed. For a 1 = 1 the erf converges against unity, corresponding to an activation of all particles as CCN at high S, which is adequate in most cases. Analogously, the double-erf fit (mode = 2) is represented by the function with index 1 and 2 specifying the variables for both modes.
To simplify the fitting procedure, a 1 = 1 was assumed. Note further that in Part 1 we tested different reference aerosol number concentrations, N CN,Dcut (e.g., N CN,10 and N CN,50 ), for the CCN efficiency spectra parametrization. In this study, we use only one reference concentration for clarity -namely N CN,10 . The choice of N CN,10 can be explained by the fact that it is experimentally rather easily accessible (e.g., via condensation particle counter, CPC, measurements), whereas reference concentrations such as N CN,50 require more elaborated experimental setups (e.g., Scanning Mobility Particle Sizer, SMPS, data).
The κ distributions were calculated according to the procedure reported in Su et al. (2010) for every individual CCN measurement cycle and subsequently averaged for time periods of interest. The corresponding N CN κ distributions were obtained by multiplication of the average κ distributions with the average N CN size distributions within the same time frame. The entire CCN analysis was conducted in IGOR Pro (Wavemetrics, Inc., Portland, OR, USA).

Backward trajectories
The backward-trajectory (BT) analysis and classification in this study has been adopted from C. , where an in-depth description of the procedure can be found. Briefly, the BT analysis is based on the Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT, NOAA-ARL) with meteorological input data from the Global Data Assimilation System (GDAS1) (Draxler and Hess, 1998). Three-day BTs have been calculated every 1 h with a starting height of 1000 m above ground level (a.g.l.) at the ATTO site for the time period of 1 January 2008 until 30 June 2016. A sensitivity test confirmed that starting heights of the BTs at 200 and 1000 m a.g.l. gave similar results. Accordingly, the chosen start height at 1000 m appears to be a good representation of the origin of the boundary layer (BL) air masses at ATTO. Subsequently, the resulting ensemble of 74 496 individual BTs was classified into 15 clusters with k-means cluster analysis (CA). Figure S1 in the Supplement shows a map of the northeastern Amazon Basin with the ATTO site and the mean track of the 15 BT clusters. It illustrates that the air masses arrive almost exclusively in a rather narrow easterly wind sector (between 45 and 120 • ). Within this sector, four main directions of air mass advection can be identified: (i) a northeasterly (NE) track including the clusters NE1, NE2, and NE3; (ii) an east-northeasterly (ENE) track including the clusters ENE1, ENE2, ENE3, and ENE4; (iii) an easterly (E) track including the clusters E1, E2, E3, and E4; and (iv) a group of "inland" trajectories in east-southeasterly (ESE) directions including clusters ESE1, ESE2, and ESE3 as well as one cluster towards the southwest (SW1). For a detailed characterization of the land cover, including potential trace gas, aerosol, and CCN sources, within the BT-derived footprint region of the ATTO site, we refer the reader to C. .

Satellite data and analysis
The satellite data products used in this study were obtained from the NASA Giovanni web interface (http://giovanni.gsfc. nasa.gov/; last access: 26 May 2017), developed and maintained by the NASA Goddard Earth Sciences Data and Information Services Center (GES DISC) (Acker and Leptoukh, 2007). The following satellite products were used: -Cloud top temperature data (AIRX3STD_v006 product) from the atmospheric infrared sounder (AIRS) instruments on board the satellites Terra and Aqua (data included from 4 July 2002 to 30 June 2016). For the corresponding time series in this study, the Aqua and Terra data were averaged per day for a representative region (i.e., ROI ATTO ; see below).
-Cloud cover data were obtained by the Moderate Resolution Imaging Spectroradiometer (MODIS) on board the Terra and Aqua satellites (included data from 4 July 2002 to 30 June 2016). The obtained Aqua and Terra time series were averaged for the ROI ATTO . Note that cloud cover strongly depends on the spatial resolution of the instrument as outlined in King et al. (2013).
-Cloud droplet effective radius, r e , data were calculated from MODIS products (included data from 4 July 2002 to 30 June 2016) for the ROI ATTO . Since r e varies with vertical cloud development and total CCN abundance, we filtered the r e data by cloud top temperature (King et al., 2013).
-Precipitation rate data, P TRMM , are obtained from the Tropical Rainfall Measuring Mission (TRMM) within the ROI ATTO . The TRMM_3B42_Daily_v7 product was used for the time period 1 January 1998 until 30 June 2016.
The satellite data were used as time series of area-averaged data products within a region of interest around the ATTO site (ROI ATTO : 3.5 • S-2.4 • N, 59.5-54 • W) as specified in Fig. S1.

Seasonal cycles of remote-sensing and in situ data
To provide an overall picture of the seasonal cycle of selected aerosol, meteorological, and cloud microphysical parameters representative for the ATTO region, various multi-year data sets were analyzed and compared. Remote-sensing data products were used in the time frames outlined in Sect. 2.4. For M BC e , c CO , and the particle concentrations in the accumulation mode range (N acc ), in the Aitken mode range (N Ait ), and in the total particle population (N CN,10 ), 4-6 years of ATTO site measurements were available. Additionally, M BC e data measured at the ZF2 site, located 40 km northwest of Manaus, were used to reflect the conditions back to 2008 (e.g., Martin et al., 2010a). In terms of sources and conditions, the ATTO and ZF2 sites are comparable (Saturno et al., 2017a;. Accordingly, combined M BC e time series from ATTO and ZF2 spanning from January 2008 to May 2017 were included here. The c CO data include ATTO measurements from March 2012 to April 2017. The N acc , N Ait , and N CN,10 data are based on SMPS measurements at ATTO from February 2014 to January 2017.
2.6 Aerosol sampling and scanning electron microscopy with X-ray spectroscopy Aerosol samples for electron microspectroscopy were collected by impaction. A homemade single-stage impactor (flow rate = 1-1.5 L min −1 ; nominal cut-off: D cut ≈ 500 nm) was used for collection. The collection efficiency below D cut decreases steeply; however, a certain fraction of particles in this size range is still collected. Moreover, a fraction of very small particles is additionally collected via diffusive deposition and therefore available for the microscopic analysis. Aerosol particles were deposited onto silicon nitride substrates (Si 3 N 4 ; membrane width: 500 µm; membrane thicknesses: 100 or 150 nm; Silson Ltd., Northhampton, UK). Immediately after sampling, samples were stored in airtight containers at −20 • C. Without further treatment like sputter coating, particles were analyzed in a high-resolution scanning electron microscope (SEM; FEI Quanta 200F, FEI, Eindhoven, the Netherlands). An acceleration voltage of 12.5 kV with a spot size of approximately 3 nm was used. X-ray emission was analyzed using energy-dispersive X-ray analysis (EDX; Edax Genesis, Edax Inc.). The system is able to record characteristic X-ray emissions for all elements with Z > 5. Obviously, in the present work Si could not be quantified due to the Si 3 N 4 substrate (Kandler et al., 2011).

Definition of empirically pristine rain forest aerosol conditions at ATTO
The term pristine is bound to a pre-human reference state with prevailing natural atmospheric conditions, in the absence of any anthropogenic influences. Andreae (2007) pointed out that in the present-day atmosphere "there are no places where we can expect to find truly pristine conditions". This is particularly true with respect to long-lived trace gases, such as CO 2 and CH 4 , which have accumulated in the atmosphere due to man-made activities. However, the aerosol abundance and composition are also substantially perturbed by anthropogenic emissions. This also includes aerosols at remote locations, which are altered to varying degrees by a globally pervasive background pollution. It has been controversially debated if and to what extent certain marine and remote continental locations still approximate pristine atmospheric conditions (e.g., Andreae, 2009;Martin et al., 2010b;Pöschl et al., 2010;Chi et al., 2013;Hamilton et al., 2014). Frequently, conditions with low anthropogenic influences are characterized as "clean" or "near pristine", although these terms are rather differently and often vaguely defined. The discussion is inherently difficult since truly pristine conditions are not available anymore to quantify how close the present-day atmosphere still gets to its original pre-human state. Accordingly, truly pristine conditions remain hypothetical, and any degree of a near-pristine state has to be defined indirectly with respect to the absence of man-made emissions.
In the Amazon Basin, aerosol conditions during most of the wet season are comparatively clean with low -though detectable -concentrations of background pollution. During the multi-month wet-season period that can overall be characterized as near pristine, certain episodes can be identified where pollution concentrations drop even further and below analytical detection limits. Under these conditions, the aerosol composition can be regarded as empirically undistinguishable from a pristine state. The present study uses these episodes to operationally define a pristine state of the aerosol composition and properties in a tropical rain forest environment, which we call empirically pristine rain forest (PR) aerosol.
The selection of a robust marker is crucial for the assessment of the PR state. In previous studies, the concentrations of BC, CO, and CN as well as the air mass origin by means of BTs have been used as corresponding markers at other locations; however all of them are characterized by certain limitations (Hamilton et al., 2014, and reference therein). For the present study, we explored the suitability of BC, CO, CN, and BTs as well as combinations of them as PR markers. Their strengths and limitations can be summarized as follows: -BT-based PR filter: BTs help to identify periods with comparatively clean air mass advection due to fact that the BTs which reach furthest to the northeast across the South American continent overpass the largest fraction of uninhibited and, thus, untouched forest regions (C. . Accordingly, a BT filter allows local and regional sources of anthropogenic pollution to be excluded. However, BTs do not allow long-rangetransport aerosols to be filtered out reliably, particularly from African sources. Accordingly, BTs are not suitable as a stand-alone PR filter; however, they are useful in combination with other PR markers as outlined below. -CN-based PR filter: the total particle concentration per se is not a good filter for clean or (near-)pristine states since natural aerosol conditions range from very low (e.g., N CN in Antarctica reaching down to 10 cm −3 ; Fiebig et al., 2014) to very high concentrations (e.g., N CN in the upper troposphere (UT) reaching above 10 000 cm −3 ; Andreae et al., 2018). Accordingly, N CN is also not a good stand-alone PR filter. However, with respect to the "typical" Amazonian aerosol concentrations in the boundary layer (i.e., a few hundred up to few thousand particles per cubic meter), the total particle concentrations provide at least a helpful reference level for the extent of pollution.
-BC-based definition of PR, called PR BC : BC represents a unique indicator for combustion aerosol particles, which in the Amazon Basin almost entirely originate from anthropogenic sources (i.e., fossil fuel and biomass burning in South American and Africa). Accordingly, we defined PR BC episodes by means of the absence of detectable BC e . Petzold and Schönlinner (2004) determined the detection limit of the MAAP "as the minimum resolvable absorbance" by considering "the variability of blank filter optical properties". The detection limit corresponds to the resulting mean absorbance of the blank filter +3× the standard deviation (SD) resulting in an absorption coefficient of 0.132 Mm −1 for 30 min averages. The M BC e was calculated by using mass absorption cross sections (MACs) retrieved by fitting MAAP absorption coefficients at 637 nm and Single Particle Soot Photometer (SP2) rBC mass measurements during the different seasons as explained in Saturno et al. (2017a, c). Using the MAC values measured at ATTO (MAC for the wet season: 11.4 ± 1.2 m 2 g −1 ; MAC for the dry season: 12.3 ± 1.3 m 2 g −1 ), the conversion to M BC e corresponds to 0.011-0.012 µg m −3 . Note that this threshold would be higher if a "traditional" MAC value of 6.6 m 2 g −1 were used to calculate M BC e (∼ 0.019 µg m −3 ). Here, we selected a threshold concentration of M * BC e = 0.01 µg m −3 when the ATTOspecific MAC values are taken into account. Accordingly, PR BC periods fulfill the criterion M BC e < M * BC e for ≥ 6 h (after applying a five-point running average to the 1 h M BC e data).
-CO-based definition of PR, called PR CO : the BC approach has the potential drawback that it may overemphasize periods with strong precipitation, since heavy rain removes the BC/aerosol content in actually polluted air masses irrespective of the gas phase composition (see Hamilton et al., 2014). Accordingly, the PR CO filter is based on the gas phase combustion marker, CO. In our definition, PR CO conditions prevailed during periods in which the ATTO c CO concentrations dropped below the monthly background CO levels at the following reference stations (https://www.esrl.noaa.gov/gmd/ dv/site/CPT.html; last access: 7 April 2018): whenever the ATTO c CO data were associated with northern hemispheric (NH) BTs (i.e., NE or ENE BT clusters, Fig. S1) and dropped below the average of the monthly CO levels obtained at the three background stations at Ragged Point in Barbados (RPB), Assekrem in Algeria (ASK), and Izaña in Cape Verde (IZO), the episode was flagged as PR CO . Analogously, whenever the ATTO c CO data were associated with southern hemispheric (SH) BTs (i.e., E and ESE BT clusters) and dropped below the monthly CO levels obtained at the background station on Ascension Island (ACS), the episode was also flagged as PR CO . Note that the time series of monthly c CO levels from the reference stations was linearly interpolated to hourly values for the comparison with ATTO c CO data. The BTs from the northern hemisphere (i.e., NE and ENE BT clusters) account for ∼ 70 % of all BTs during the wet season. Among these ∼ 70, ∼ 30 % can be attributed to the NE BT clusters. The locations of the CO background stations, the wet-season ATTO BT ensemble, and the hemispheric CO distribution are shown in Fig. S2.
The seasonality in the frequency of occurrence, f , of the PR BC and PR CO filters is generally very similar, as shown in Fig. 1: the first PR BC and PR CO episodes occur in February. Their highest f is reached around the second half of April and the first half of May. Afterwards, f decreases steeply and PR conditions occur only occasionally in June and July. Overall, PR BC and PR CO episodes overlap ∼ 25 % of the total time that is flagged by at least one of the two filters. Since both approaches are associated with certain limitations and uncertainties, we further analyzed two combinations of PR BC and PR CO : the union of both sets (PR BC ∪ CO ) and the intersection of both sets (PR BC ∩ CO ) as shown in Fig. 1. For the in-depth analysis of aerosol and CCN properties in this work, we chose the PR BC ∩ CO filter, which we consider as the most strict and, thus, robust since the criteria of both filters have to be fulfilled. With respect to the PR filters, the following aspects are worth mentioning: PR episodes at ATTO exclusively occur during the wet season due to a combination of two effects. First, the ATTO site is very remote and the characteristic wet-season air mass advection occurs mostly over uninhabited areas (see C. . Second, the high precipitation rates entail strong scavenging and, thus, relatively short aerosol particle lifetimes, which reduces the long-range transport of the background pollution aerosol load. In contrast, dry-season PR episodes have almost never been observed at ATTO due to the extensive biomass burning emissions in South America and Africa in combination with low scavenging rates and, thus, long atmospheric aerosol lifetimes. This is relevant since wet-vs. dry-season conditions were likely associated with different atmospheric states, for example with respect to volatile organic compound (VOC) concentrations and aerosol populations as well as photochemical conditions. While wet-season PR states are still experimentally accessible as outlined in this work, the dryseason PR state appears to be entirely swamped by pollution.
The primary filters are based on the combustion markers BC and CO, which do not allow a discrimination between wildfires and man-made fires. Accordingly, the contribution of wildfire emissions, which were part of an originally pristine atmosphere in the Amazon, is erroneously filtered out. Generally, wildfires in the tropical Amazonian forests are rare events due to the fact that the dense and moist canopies -if unperturbed -effectively maintain a fire-immune state (e.g., Cochrane, 2003;Nepstad et al., 2008). Nevertheless, wildfires play a certain, although minor, role for the ATTO observations, since the wet-season BTs cover the Guianan savanna ecoregions that account for ∼ 8 % of the ATTO footprint region (Olson et al., 2001;. Within these regions, the infrequent occurrence of wildfires is part of the savanna-specific fire regime (de Carvalho and Mustin, 2017). Figure S3 illustrates the relevance of wildfires for ATTO under wet-season conditions. Moreover, Saharan dust as well as marine aerosols from the Atlantic Ocean are advected towards the ATTO region via wet-season LRT plumes, which are most frequent in February and March . Saharan dust and marine aerosols can also be considered as part of an original pristine atmospheric state in the Amazon. However, all LRT plumes arriving at ATTO are filtered out by the PR BC and PR CO approaches due to the fact that virtually all LRT plumes contain a substantial fraction of smoke from mostly man-made fires in West Africa . Accordingly, the role of the present-day LRT plumes arriving at ATTO has to be differentiated carefully as they represent a (partly internal) mixture of natural and anthropogenic aerosols.
3 Results and discussion

Aerosol and cloud microphysical seasonality in the Amazon
Prior to the in-depth analysis of the aerosol and CCN cycling for characteristic conditions, this section provides an overview of the aerosol and cloud microphysical seasonality in the ATTO region. The pollution markers c CO and M BC e in Fig. 2a show a pronounced seasonal cycle with a prevalence of clean conditions in the wet season vs. the biomassburning-related pollution maximum in the dry season (Andreae et al., 2015). The annual minimum in M BC e levels occurs at the end of April (with weekly M BC e means of ∼ 0.03 µg m −3 ), whereas its highest concentrations were observed in August and September (with weekly M BC e means of ∼ 0.40 µg m −3 ). The seasonal cycle of c CO shows a temporal shift of about 1 month with its minimum in the beginning of June (with weekly c CO means ∼ 100 ppb) and largest values from October to December (with weekly c CO means ∼ 200 ppb). The phase shift between the c CO and M BC e seasonality can be explained by the spatiotemporal interplay of combustion-related BC and CO sources, aerosol wet scavenging, and alternating advection of NH vs. SH air masses (Martin et al., 2010b;Andreae et al., , 2015. Similar to the M BC e trends, the total aerosol particle concentration, N CN,10 , tracks the seasonality in biomass burning activities (in South America and Africa) with lowest concentrations in March and April (N CN,10 weekly means from 200 to 300 cm −3 ) and highest values between August and November (N CN,10 weekly means from 1000 to 2000 cm −3 ) as shown in Fig. 2b. The CCN concentrations at a supersaturation of 0.5 %, N CCN (0.5 %), which were calculated based on long-term SMPS data and the κ-Köhler parametrization as outlined in our Part 1 paper, mostly tracked the seasonal trends in N CN,10 . Its minimum around March and April showed weekly mean N CCN (0.5 %) values around 200 cm −3 , whereas the maximum showed values between 1000 and 2000 cm −3 . Figure 2c shows the seasonal cycles of two precipitation data products: first, P TRMM data represent the area-averaged precipitation rate in the ROI ATTO (see Fig. S1). The P TRMM data reveal a rather broad wet-season precipitation maximum from March to May. The smallest precipitation rates are observed from September to November. Second, the P BT data (c) Precipitation products, P BT , representing cumulative precipitation along BT tracks, and P TRMM , representing TRMMderived precipitation within the ROI ATTO as defined in Fig. S1. represent the cumulative precipitation along the BTs arriving at ATTO (for details see C. . Thus, P BT represents a measure for the extent of rain-related aerosol scavenging -particularly of long-range-transport aerosolsduring air mass transport towards ATTO. A pronounced maximum in P BT and the related scavenging is observed for the months April and May, which coincides with the minimum in aerosol parameters (i.e., M BC e and N CN,10 ) (see also Moran-Zuloaga et al., 2017). Figure 2d shows the seasonal cycles in cloud fraction and cloud top temperature within the ROI ATTO . Both are predominantly influenced by the position of the ITCZ with its belt of extended deep convective cloud systems and strong precipitation (e.g., Moran-Zuloaga et al., 2017). According to Fig. 2d, the densest cloud cover and deepest convection (represented by lowest cloud top temperature) occurs upon northerly passage of the ITCZ in the middle of the wet season (i.e., March and April) as well as upon southerly passage of the ITCZ at the end of the dry season (around November). The maximum in deep convection in March and April -expectedly -corresponds to the peak in P TRMM . A global picture of the spatiotemporal trends in cloud microphysical properties can be found in King et al. (2013). Figure 2e presents the satellite-derived effective radius, r e , of liquid cloud droplets that links the seasonality in aerosol and cloud properties. The r e data have been filtered by cloud top temperature to discriminate the different r e growth states at different heights of the convective clouds. It is well established that increased CCN loads entail an influence on cloud properties, which typically results in a corresponding decrease in droplet diameter (e.g., Freud et al., 2008;Stevens and Feingold, 2009). Figure 2e underlines this behavior by means of a clear seasonality in r e with its maximum during the clean wet season (i.e., April and May) and its minimum during the polluted dry season (i.e., August to November). A detailed understanding of the impact of the CCN loading on the cloud microphysical properties, however, is the subject of ongoing studies at ATTO and further locations worldwide.
In essence, Fig. 2 provides a coherent picture of the aerosol, cloud, and precipitation seasonality as well as their corresponding linkages. The following sections will zoom into this overall picture by presenting detailed aerosol and CCN data from characteristic wet-and dry-season conditions of the year 2014.

Aerosol and CCN time series for representative wet-season conditions
During the Amazonian wet season (February to May), the influence of local and regional anthropogenic pollution (i.e., from biomass burning) decreases to a minimum, and simultaneous strong precipitation causes efficient aerosol scavenging (see Fig. 2). The combination of both effects results in a comparatively clean state of the Amazonian atmosphere (Martin et al., 2010b;Andreae et al., 2015). During this time of the year, biogenic aerosols from the surrounding rain forest ecosystem, such as secondary organic aerosol (SOA) from the oxidation of biogenic volatile organic compounds (BVOCs) as well as primary biological aerosol particles (PBAP), prevail Huffman et al., 2012;Yañez-Serrano et al., 2015). However, the regionally and biogenically dominated background state of the atmosphere is frequently perturbed by the episodic advection of LRT aerosols from Africa in air masses that bypass the major rain fields and, therefore, "survive" the intense scavenging . The frequent intrusion of LRT aerosols is a characteristic feature during the Amazonian wet season and represents a strong and important influence on the rain forest ecosystem (e.g., Chen et al., 2009;Bristow et al., 2010;Baars et al., 2011;Abouchami et al., 2013;Yu et al., 2015;Rizzolo et al., 2017). These LRT plumes mostly comprise a complex mixture of Saharan dust, African biomass burning smoke, and marine aerosols from the transatlantic air passage (e.g., Talbot et al., 1990;Swap et al., 1992;Gläser et al., 2015). The 2-month period in Fig. 3 can be regarded as representative for typical wet-season conditions in the ATTO region as it includes both scenarios: periods with a prevalence of the local (biogenic) background aerosol and episodes under the influence of LRT plumes, as well as intermediate states.
In general, the wet season of 2014 showed average hydrological conditions without significant precipitation anomalies within the ROI ATTO , which is in stark contrast to 2015/16 with its pronounced El Niño influence and an associated negative precipitation anomaly (see C. Saturno et al., 2017a). Furthermore, the pollution tracers -N CN,10 , M BC e , and c CO -showed comparatively low values with concentrations around N CN,10 = 330 ± 130 cm −3 , M BC e = 0.03 ± 0.05 µg m −3 , and c CO = 110 ± 10 ppb (given as mean ± 1 SD for the entire time period in Fig. 3) in agreement with previous studies (e.g., Andreae et al., , 2015Artaxo et al., 2013). In terms of atmospheric circulation, the first half of the 2-month time frame was dominated by backward-trajectory arrivals from the northeast (blue and green BT clusters; see Figs. 3a and S1), whereas during the second half the dominant wind direction shifted towards easterly directions (orange and red BT clusters; see Figs. 3a and S1) (compare Andreae et al., 2015;. This gradual swing of the dominant wind direction from NH to SH relates to the northwards movement of the ITCZ. In Fig. 3, the orange background shading emphasizes several episodes with detectable LRT influence, according to Moran-Zuloaga et al. (2017). A comparatively strong LRT plume at ATTO -labeled as LRT case study in Fig. 3 -is the subject of a detailed CCN analysis in Sect. 3.5. The interested reader will find further in-depth analysis of this particular LRT event in Moran-Zuloaga et al., 2017 (where it is discussed as event "2014_7").  argued that the "atmospheric state and processes in the Ama- zon Basin cannot be understood without the consideration of pollutant inputs by long-range transport". This is evidently true for the major LRT plumes in Fig. 3 with M BC e reaching up to 0.3 µg m −3 as well as associated increases in N acc . However, a closer analysis of the extended and relatively clean period from 14 April until 31 May 2014 also reveals that during ∼ 85 % of the time detectable amounts of background pollution were present (i.e., M BC e exceeding M BC e * ; see Sect. 2.7). Although (highly) diluted, the advected aerosols can impact the CCN population, as discussed in Sect. 3.4. Only when pollution levels actually drop below detection limits and the conditions satisfy our rather strict PR BC ∩ CO filter do empirically pristine aerosol conditions prevail, which are emphasized by a blue shading in Fig. 3. A statistical overview of the relative fraction of PR episodes for the years 2012 to 2016 is shown in Fig. 1. It shows that PR conditions typically occur from March to May, with their highest abundance around late April and early May, when weekly frequencies of occurrence reach up to ∼ 20 %, according to the strict PR BC ∩ CO filter, or even higher. Note that the PR episodes in 2014 mostly occurred in April and May (compare Figs. 3 and S4), which is in good agreement with the multi-year observations.
The following picture emerges for the CCN parameters: the time series of the κ(S, D a ) size distributions in Fig. 3d clearly illustrates the different κ(S, D a ) of Aitken and accumulation modes as discussed in our Part 1 study . Overall, κ(S, D a ) shows a clear variability for low S, representing the accumulation mode, and rather stable values for higher S, representing the Aitken mode (see Fig. 3h). The occurrence of the LRT plumes stands out clearly by causing a significant enhancement of κ(S, D a ), with κ Acc reaching 0.4 and κ Ait reaching 0.25 (see Fig. 3d and h). Moreover, the LRT events are also associated with increased N CCN (S) and N CCN (S)/N CN values ( Fig. 3g and i). Note that the occurrence of the LRT events precisely coincides with the minima in P BT and, thus, "windows" in aerosol scavenging (see Moran-Zuloaga et al., 2017).
For the extended and comparatively clean period from 14 April until end of May, the SMPS contour plot (Fig. 3c) reveals equally strong Aiken and accumulation modes as well as a "patchy" appearance, due to frequent rainfall causing (local) aerosol scavenging. As outlined in Part 1, the aerosol abundance in the particle size range > 40 nm predominantly defined the measured CCN population . Accordingly, the N CCN (S) and N CCN (S)/N CN time series directly track the SMPS-derived patchy pattern. The low S levels (i.e., N CCN (0.11 %)), which do not activate Aitken mode particles, closely followed the accumulation mode concentration, N acc , time series, whereas the higher S levels (i.e., N CCN (1.10 %)), which also activated particles in the Aitken mode, closely tracked N CN,10 (= N Ait + N acc ). Two of the subsequent case studies will focus in more detail on the specific CCN properties of the PR (Sect. 3.4) and LRT (Sect. 3.5) conditions (see also Table 1).

Aerosol and CCN time series for representative dry-season conditions
During the dry season (August to November), the central Amazon is under continuous influence of pronounced anthropogenic pollution. The predominant type is biomass burning smoke from deforestation fires, which led to the coining of the term "biomass burning season" (Freud et al., 2008). In addition, various urban and industrial emission sources in eastern and southern Brazil as well as southern Africa may also contribute by hard-to-define quantities (e.g., Andreae et al., 1994;Saturno et al., 2017a). The minimum in precipitation rates and, thus, in aerosol scavenging fosters the distribution of pollution aerosols over large areas by extending their atmospheric lifetime (see Fig. 2). Figure 4 represents the dry-season counterpart of Fig. 3 and shows the corresponding time series for a characteristic dry-season period from 1 August until 30 September 2014. The BT clusters in Fig. 4a show that easterly and southeasterly BTs prevailed, since the ITCZ was located north of the ATTO site. The BT clusters which are most characteristic for the dry season approached the Amazon River delta from the South Atlantic and then followed the river in a westerly direction towards ATTO (red and orange clusters; see Fig. S1). These "dry-season river BTs" are the subject of a more detailed discussion in the case study in Sect. 3.7. For certain episodes, the wind swings further to southeasterly directions and brings air masses from inland directions (black, brown, and grey BT clusters; see Fig. S1). These "dry-season inland BTs" are further discussed in the case study in Sect. 3.6.
In contrast to the wet season, the accumulation mode clearly dominates the size distribution, which explains the increased CCN efficiencies, particularly at low S ( Fig. 4c and i). The frequent "pulses" in the accumulation mode concentration can be attributed to (aged) biomass burning plumes, which impact the ATTO site episodically, typically for few days (see Freitas et al., 2005). The M BC e , N CN,10 , and c CO levels are typical for dry-season conditions in the northeast Amazon Basin with M BC e = 0.55 ± 0.35 µg m −3 , N CN,10 = 1520 ± 780 cm −3 , and c CO = 140 ± 50 ppb (given as mean ± 1 SD for the time period in Fig. 4) (e.g., Rissler et al., 2004;Andreae et al., , 2015Artaxo et al., 2013;Saturno et al., 2017a).
The most obvious event in Fig. 4 is the advection of a strong BB plume from 17 to 23 August 2014, the highest pollution levels that were observed during the entire CCN measurement period. This event can be recognized by means of strong pulses in N Acc , M BC e , and c CO as well as a dip in κ(S, D a ). The ACSM-derived organic-to-sulfate ratio confirms that the biomass burning pulse comprised a predominantly organic aerosol. In general, the measured κ(S, D a ) levels respond inversely to the organic-to-sulfate ratio, confirming previous studies which stated that organic matter and sulfate constituents mostly define the aerosol's hygroscopicity in the Amazon (Roberts et al., 2002;Gunthe et al., 2009).   (Table 3).
-BB episode highlighted in Fig. 4 and shown in detail in Fig. 8.  (Table 3).
(in dry season) (for details refer to Fig. 9) -MPOL highlighted in Fig. 4 and shown in detail in Fig. 9. The major biomass burning plume in August 2014 is the subject of the detailed case study BB in Sect. 3.6.
Beside this major biomass burning plume, several shorter pulses, which were supposedly also caused by upwind fires, were observed throughout the dry-season period, and their frequency of occurrence increased towards the end (i.e., after 12 September). Phenomenologically, the major and minor biomass burning plumes were similar as they exhibit peaks in N CN , M BC e , and c CO and simultaneous dips in κ(S, D a ) and the organic-to-sulfate ratio. The second half of September comprised conditions with comparatively high sulfate concentrations and a sequence of short biomass burning plumes. This period is influenced by a mixture of different (pollution) aerosol populations from African long-range transport and regional South American sources. A detailed description of the case study MPOL can be found in Sect. 3.7.
Similar to the wet season, different κ(S, D a ) levels for the Aitken and accumulation modes as well as comparably low κ(S, D a ) variability over time (κ Ait = 0.14 ± 0.03 vs. κ Acc = 0.23 ± 0.04, covering the entire time period in Fig. 4d and h) were observed. The MAF(S) values tend to reach unity, except for MAF(0.11 %) under the influence of biomass burning smoke (i.e., for the smaller and major smoke plumes).

Case study PR on empirically pristine rain forest aerosols
Aerosol-cloud interactions remain the largest uncertainty in global climate models, and a better understanding of a preindustrial atmospheric state is essential to reduce this uncertainty (Carslaw et al., 2013;Seinfeld et al., 2016). As outlined in Sect. 2.7, the Amazonian wet season provides the rare chance to analyze episodes of very clean continental conditions, which are our best approximation of a pristine rain forest atmosphere. This case study extracts the characteristic aerosol and CCN properties during the identified PR periods. Figure 5 zooms into three selected episodes -called PR1, PR2, and PR3 as highlighted in Fig. 3 -and combines meteorological, aerosol, and CCN time series for a detailed analysis. The meteorological parameters in Fig. 5a, b, and c illustrate typical wet-season conditions: (i) a rather high degree of cloudiness, which can be seen by means of the strong cloud-related dimming of the incoming shortwave radiation, SW in ; (ii) frequent local (P ATTO ) and regional (P TRMM ) rain events; (iii) a comparatively stable northeasterly wind direction, which is consistent with the BT analysis in Fig. 3; (iv) a rather constant wind speed, U , for most of the time, which got more vigorous during rain events; (v) high-relativehumidity (RH) conditions, being inversely related to SW in and reaching saturation during the nights; and (vi) a characteristic time series of the equivalent potential temperature, θ e , which tracked the daily onset of solar heating (see simultaneous increase of SW in and θ e ) and further provides valu-able information on vertical atmospheric mixing, particularly in connection with rain events. Specifically, sudden drops in θ e indicate a downward transport of air masses from uppertropospheric layers, which occurred frequently with the onset of strong rain (for more details see Wang et al., 2016).
The corresponding aerosol variability is shown as an aerosol number size distribution (dN/dlogD) contour plot in Fig. 5d. Under PR conditions we found a dominant Aitken mode and a comparatively weak accumulation mode, as reported previously (e.g., Andreae et al., 2015;Pöhlker et al., 2016). Moreover, the Aitken and accumulation modes reveal a patchy and discontinuous abundance with rather sudden concentration increases and drops. These observations can be explained by a combination of different effects and processes: first, the strong and persistent (mostly combustionrelated) sources of accumulation mode aerosol particles, which are responsible for the continuous and dominant accumulation mode in the dry season, were absent.
Second, the frequent rain events acted as an efficient aerosol removal mechanism via aerosol rain-out (i.e., particle activation into cloud/rain droplets) and wash-out (i.e., particle collection by falling droplets below clouds). The washout efficiency is slightly higher (∼ factor 1.5) for Aitken than accumulation mode particles (Wang et al., 2010;Zikova and Zdimal, 2016). In contrast, the rain-out efficiency, corresponding to CCN activation, is typically much higher for accumulation than Aitken mode particles . Accordingly, the rain pulses strongly modulated the aerosol's abundance via sudden and efficient deposition, which is visible in Fig. 5d as characteristic "notches" in the aerosol contour plot. The notches represent the (removed) part of the aerosol size fraction that was activated as CCN into cloud droplets. Illustrative examples can be found during days with strong rain showers, such as 27 April, 5 May, and 6 May. Note that the "depth of the notches", corresponding to the smallest activated particles, could in principle be used to estimate the S levels during the corresponding events (Krüger et al., 2014). Further note in this context that, besides depletion of the accumulation relative to the Aitken mode, aerosol activation and cloud processing are also known to foster the opposite effect: the growth of Aitken mode particles into the accumulation mode via formation of aqueous-phase reaction products (i.e., sulfate and aqueous-phase SOA) in the cloud droplets, followed by droplet re-evaporation and deposition of the newly formed compounds onto the particles (e.g., Ervens, 2015;Farmer et al., 2015). During 7 May, cloud processing might have been responsible for the formation of a rather strong accumulation mode from an existing Aitken mode population.
As a third process, the Aitken mode population in the rain forest BL was frequently replenished by pulse-like appearance of particles with diameters < 50 nm. These events are supposed to be convection-related downward transport of air masses from an UT particle pool and the subsequent growth of the injected fine particles Andreae Figure 5. Selected meteorological, aerosol, and CCN time series from ATTO measurements for the empirically pristine rain forest (PR) case study periods PR1, PR2, and PR3 (see Fig. 3).  , 2018). Remarkably, the combination of all these effects results in a comparatively constant total particle abundance, N CN , across the rain showers, due to compensating effects of accumulation mode particle losses and simultaneous increases in Aitken mode abundance (see details in Wang et al., 2016). The convection-related downward transport of fine UT particles and their subsequent growth -presumably by the condensation of low-volatility vapors -is a characteristic feature of the Amazonian wet season. At least three pronounced examples for this process are included in the time frame of Fig. 5 (i.e., 27/28 April, 4/5 May, and 16/17 May). After their injection into the forest BL, the fine particles (initial diameters between 20 and 50 nm for the events in Fig. 5) reveal a "banana-like" growth into the Aitken mode size range (∼ 70 nm) in the course of about 12-24 h. For the events in Fig. 5, we calculated an initial, and thus maximum, growth rate of 0.6 to 6 nm h −1 , which agrees well with the 1 to 6 nm h −1 reported by Kulmala et al. (2004) for tropical regions as well as the reported 5 nm h −1 in Zhou et al. (2002) for an Amazonian site. Note that these "Amazonian bananas" differ from the classical new-particle formation (NPF) events that have been reported for various continental sites (i.e., in northern hemispheric temperate regions) (Kulmala et al., 2004), since the number concentrations are lower by orders of magnitude and their nucleation and initial growth do not occur in the BL but in the UT Engstrom et al., 2008;Pöschl et al., 2010;Andreae et al., 2018). Accordingly, the UT particle population that is frequently injected into the BL is already aged to a certain extent and, thus, presumably reflects chemical processes different from the atmospheric chemistry in the BL. The physicochemical details of the UT nucleation and growth are still largely unknown and the subject of ongoing research (e.g., . The CCN properties during PR conditions are represented by time series of κ(S, D a ) size distributions (Fig. 5d) and N CCN (S) for two selected S (Fig. 5e). The temporal pattern of the κ(S, D a ) size distributions, which provides indications of the aerosol particles' chemical composition, reflects the pattern of the underlying dN/dlogD contour plot. Consistent with our observations in Part 1 , the accumulation mode reveals higher κ(S, D a ) levels than the Aitken mode, likely due to chemical aging through cloud processing and a related increase in hygroscopicity (Farmer et al., 2015). The lowest κ(S, D a ) levels were observed for the "Amazonian bananas" (see Fig. 5d). Both the accumulation and Aitken mode κ(S, D a ) levels show a variability that tracks the Aitken and accumulation mode abundance. Note that N CCN (0.5 %) and particularly N CCN (0.2 %) show pronounced increases during periods with increased M BC e levels (e.g., 25 April, 5 May, and 17 May). This emphasizes the remarkable impact of diluted pollution on the CCN population in an aerosol-limited regime according to Reutter et al. (2009). Figure 6a and b summarize the average aerosol and CCN key properties under PR conditions. 1 Figure 6a shows the characteristic average N CN (D) size distribution with a pronounced bimodal appearance, comprising a dominant Aitken mode (D Ait ≈ 70 nm, N Ait ≈ 160 cm −3 ) and a comparatively weak accumulation mode (D acc ≈ 160 nm, N acc ≈ 90 cm −3 ) (see Table 2). This bimodal shape is typical for clean Amazonian conditions as reported previously (e.g., Gunthe et al., 2009) and further resembles aerosol size distributions under marine background conditions (e.g., Atwood et al., 2017). The corresponding N CCN (S,D) size distributions for all S levels show that for S < 0.3 % mostly accumulation mode particles were activated, whereas for S > 0.3 % the Aitken mode particles also acted as CCN. Furthermore, Fig. 6a shows the average κ(S, D a ) size dependence with a characteristic stepwise increase of κ(S, D a ) towards larger D. The Aitken mode κ(S, D a ) levels are rather low and sharply defined (mean ± SD: 0.12 ± 0.01), whereas the accumulation mode κ(S, D a ) levels are slightly higher (0.18 ± 0.02). The results suggest that the Aitken mode particles, which are frequently injected into the BL via downward transport from the UT, are mostly comprised of organic matter. This observation agrees well with recent results showing that "the UT particles consist predominantly of organic material, with minor amounts of nitrate and very small fractions of sulfate" . The hygroscopicity of organic material, κ org , is typically assumed as ∼ 0.10; however, κ org can vary substantially (close to 0 up to 0.3) as a function of the organic material and its oxygen-to-carbon (O : C) ratio Thalman et al., 2017). The κ(S, D a ) levels of the accumulation mode similarly indicate the presence of predominantly organic particles, albeit with somewhat more inorganic constituents than in the Aitken mode. This is consistent with the corresponding ACSM results in 1 The aerosol and CCN key properties are similar for all PR filters (i.e., PR BC , PR CO , PR BC ∪ CO , PR BC ∩ CO ; see Sect. 2.7). For completeness, the N CN (D) and κ(S, D a ) size distributions for all four PR filters are summarized in Fig. S5. For comparison, Fig. S6 shows N CN (D) size distributions after a classification by means of a statistical analysis of the total aerosol concentrations, which resemble the PR filter-based results. Furthermore, Fig. S7 shows the corresponding N CN (D) and κ(S, D a ) size distributions filtered for the comparatively clean BT clusters NE1, NE2, and NE3. Table 3, underlining that organic matter accounts for most of the mass (90 %), whereas nitrate (4 %) and sulfate (6 %) add only small contributions. Note that M NH 4 , M Cl , and M BC e were below the detection limit for PR conditions and were omitted in the calculation of the mass fractions accordingly (see Sect. 2.1). 2 A predicted average hygroscopicity parameter, κ p , of 0.16 ± 0.01 was calculated based on the ACSM results -excluding M NH 4 , M Cl , and M BC e -and agrees with the measured value of κ(0.11 %) = 0.18 ± 0.05 (Table 3). Figure 6b displays the CCN efficiency spectrum for PR conditions, which can be regarded as the CCN signature of the corresponding aerosol population (for details refer to the Part 1 companion paper). The pronounced bimodal particle size distribution with its characteristic Hoppel minimum and the stepwise increase of κ(S, D a ) (see Fig. 6a) result in a weak plateau at about S = 0.4 %, which required to apply a double-erf fit. For comparison, we also applied a single-erf fit. Expectedly, the double-erf fit is the better representation of the experimental data, although the single-erf fit also covers the data reasonably well, since the plateau is not particularly pronounced. However, a closer look reveals differences between the single-and double-erf fits for low and high S. For very low S (< 0.1 %), the double-erf fit indicates that the PR aerosol particles start acting as CCN only above about S = 0.06 %, which can probably be explained by the absence of suitable CCN in the size range of several hundred nanometers, which are indeed comparatively sparse under PR conditions according to Fig. 5. However, this size range was not covered directly by our CCN measurements, making it hard to draw conclusions. Since the double-erf fit describes the data more accurately than the single-erf fit, its extrapolation for S > 1.1 % is likely more accurate and suggests that "full" activation (∼ 90 %) is reached at S ≈ 1.5 %.
The CCN efficiency spectra represent a tool with which to visualize characteristic differences in the behavior of certain (contrasting) aerosol populations in cloud formation. Of particular relevance is the slope of the CCN efficiency spectra, d(N CCN (S)/N CN,10 )/dS, as the sensitivity of the activated CCN fraction of a given aerosol population within a given S range to changes in supersaturation, S. Accordingly, high d(N CCN (S)/N CN,10 )/dS slopes indicate a regime in which even a subtle S has relatively strong effects on the N CCN (S) and, thus, N d concentrations (assuming constant N CN,10 ), whereas low d(N CCN (S)/N CN,10 )/dS values indicate a regime that is characterized by more stable N CCN (S) and N d concentrations, even upon large S.
The CCN efficiency spectra can be linked to a concept introduced by Reutter et al. (2009), which classifies the sensitivity of N d concentrations in response to changes in N CN and w b . This results in three distinct regimes: (i) an aerosol-limited regime, which is characterized by high S max (> 0.5 %), a high w b / N CN ratio, high activated fractions The error bars at the markers represent the measurement error in S and 1 SD in the N CCN (S)/N CN,10 dimension. The shading represents the uncertainty of the fits. An overview of the erf fits from all case study conditions and seasonal averages can be found in Fig. 11. The parameters of all erf fits are summarized in Table 4. Data for PR conditions in (a) and (b) represent averages of all PR BC ∩ CO episodes during the entire CCN measurement period as defined in Sect. 2.7. For the PR CCN efficiency spectrum, the double-erf fit is the better representation, although the single-erf fit also works as a good approximation. Data for LRT conditions, shown in (c) and (d), represent the LRT3 period as shown in Fig. 3. A single-erf fit describes the experimental data accurately. Data for BB conditions, shown in (c) and (d), represent the time period in August 2014 as shown in Fig. 4. For the BB case, the experimental data have been fitted with a single-erf fit with two modifications: (i) the "default" fit with predefined variable a 1 = 1 as utilized for all other case studies tends to overestimate N CCN (S)/N CN,10 at high S; (ii) a corresponding fit with a free variable a 1 describes the experimental data more accurately. Data for MPOL conditions were separated into a MPOL-LRT case (g), representing sulfate-rich African aerosols, and a MPOL-BB case (h), representing plumes from close-by fires. MPOL CCN efficiency spectra are combined in (i) including single-erf fits. All fit parameters of the erf fits shown here are summarized in Table 4. The colors of the CCN efficiency spectra were chosen according to Wong (2011). Table 2. Properties (position, x 0 ; integral number concentration, N CN ; width, σ ) of Aitken and accumulation modes from single or double lognormal fits of the total particle size distribution. Values are given as means of the case study periods, whereas corresponding seasonally averaged results can be found in the Part 1 study. The errors represent the uncertainty of the fit parameters. No meaningful double lognormal fit was obtained for the monomodal MPOL case -thus, a single lognormal fit was conducted to describe the properties of the main peak. For the cases PR BC ∩ CO and LRT with clearly resolved bimodal size distributions, values for the position of the Hoppel minimum, D H , as the intersection of fitted and normalized modes as well as estimated average peak supersaturation in cloud, S cloud (D H , κ), according to Krüger et al. (2014) and Part 1 study are listed. The error in S cloud (D H , κ) is the experimentally derived error in S. Analogous information for the PR BC , PR CO , and PR BC ∪ CO filters can be found in Table S1.

Conditions
Mode or   Table 4) can be characterized as aerosol-limited, due to the overall low abundance of potential CCN. However, the CCN efficiency spectrum in Fig. 6b suggests that the PR aerosol population also has a certain sensitivity to w b , since changes in updraft velocity w b -and the associated S (even for S > 1 %) -strongly modulate the activated fraction, N CCN (S)/N CN,10 . In this sense, the PR CCN efficiency spectrum has a very characteristic shape and differs clearly from the other conditions, as it keeps increasing over a wide S range with a somewhat larger slope for S < 0.3 % and a slightly decreasing slope for S > 0.3 %. 4 Accordingly, the PR case appears to be aerosol-and updraft-sensitive, which makes the corresponding aerosol-cloud interactions highly dynamic. For more quantitative insights, modeling runs according to Reutter et al. based on the characteristic PR bimodal N CN (D) size distribution in Fig. 6a as well as adjusted N CN and w b ranges are required.

Case study LRT on Saharan dust, African smoke, and Atlantic marine aerosols
The African continent is of significant importance for the Amazonian atmospheric composition as it represents a major source of desert dust and pollution aerosols (e.g., Swap et al., 1992;Andreae et al., 1994;Yu et al., 2015;Rizzolo et al., 2017). A systematic overview of the properties and relevance of LRT plume arrivals in the ATTO region during the Amazonian wet season can be found in Moran-Zuloaga et al. (2017). Furthermore, a general characterization of the CCN population's response to LRT conditions during the wet season can be found in our Part 1 paper . ranged below the instrument detection limit in certain cases, which makes the corresponding results unreliable. The predicted average aerosol hygroscopicity parameter, κ p , was calculated according to the Part 1 study  and is shown as mean ± SE. The κ(0.10 %) results are shown with the experimentally derived error. Analogous information for the PR BC , PR CO , and PR BC ∪ CO filters can be found in Table S2.  conditions according to present work, (ii) seasonal averages from the Part 1 companion paper , and (iii) CCN efficiency spectra adapted from Roberts et al. (2001) and Andreae et al. (2004). A reference concentration ofN CN,10 has been used in all cases. N CN is shown as mean ± SE. The errors in S mode and w mode represent the uncertainty of the fit parameters (see Sect. 2.2). All CCN efficiency spectra are plotted in Fig. 11 Figure 7. Selected meteorological, aerosol, and CCN time series from ATTO measurements for the long-range-transport (LRT) study period (see Fig. 3). Based on these previous studies, the present paper analyzes the characteristic impact of LRT plumes on the wet-season CCN population in detail. The characteristic impact of LRT plumes on the aerosol and CCN data can already be seen in Fig. 3. For a detailed analysis, the strongest LRT episode in Fig. 3 has been chosen and is represented in Fig. 7 by selected meteorological, aerosol, and CCN time series. Note that the advected dust plumes typically cause clear increases in both the coarse mode, which plays a secondary role here, and the accumulation mode, which explains their relevance for the CCN variability . The LRT influence is visible in Fig. 7 by means of increases in M BC e (due to the LRT plume's smoke component), in the accumulation mode abundance in the dN/dlogD contour plot, in the concentrations N CN and N CCN (S), and in κ(S, D a ).
The plume's influence on the ATTO site lasted for about 4 days, with its onset on 9 April ∼ 12:00 and its end on 13 April ∼ 12:00, which is in good agreement with the corresponding remote-sensing data in Moran-Zuloaga et al. (2017). During these 4 days, meteorology determined the variability of the LRT aerosol in the rain forest BL via air mass advection (i.e., wind speed and direction), rain-related scavenging (i.e., P ATTO and P TRMM ), and convective mixing (represented by SW in as a proxy). Throughout the LRT period, the dominant wind direction was mostly NE to E, which is characteristic for wet-season conditions (compare Fig. 3). Note that the BTs arriving from the NE are particularly prone to bringing dust-laden air into the ATTO region . Furthermore, only few (major) rain events and related aerosol scavenging occurred during this time, which is a further prerequisite for efficient LRT transport. The arrival of the LRT plume during afternoon hours of 9 April occurred via convective downward mixing of the aerosol into the forest BL (see simultaneous increases in SW in , θ e , and the accumulation mode in dN/dlogD), and its influence lasted until 13 April, when the concentration time series decreased gradually. Note that the advected LRT plumes are transported into the ATTO region as compact and stratified aerosol layers up to altitudes of 2-3 km . Aerosol concentrations were highest during the afternoon hours on 9, 10, and 11 April, when convection (see SW in ) is most efficient in mixing the aerosols downward into the BL. Furthermore, a sudden rain-related air mass change, lasting for about 12 h (see wind direction and θ e changes) at the end of 9 April/beginning of 10 April, was associated with a simultaneous drop in LRT aerosol concentrations. The CCN population responded noticeably to the injection of the LRT event, which can be seen in N CCN (S), N CCN (S)/N CN,10 , and κ(S, D a ) in Fig. 3. Figure 7 displays the N CCN (0.2 %) and N CCN (0.5 %) time series, which show a 2-to 3-fold increase upon LRT aerosol intrusion. Moreover, the κ(S, D a ) data can be used as an indirect measure for the aerosol chemical composition, reflecting the average ratio of organic to inorganic constituents in the particles. In Fig. 7d, the occurrence of elevated κ(S, D a ) levels coincides with the variability in dN /dlogD. For this particular event, κ Acc increased from ∼ 0.3 to ∼ 0.4, whereas κ Ait increased from ∼ 0.15 to ∼ 0.25. Figure 6c summarizes the characteristic N CN (D) and N CCN (S,D) size distributions as well as the size dependence of κ(S, D a ) during LRT influence. In general, the comparison of Fig. 6a and c contrasts the characteristic LRT vs. PR conditions and emphasizes that the intrusion of African LRT plumes into the wet-season BL has significant influence on the aerosol and CCN populations. Specifically, the accumulation mode under LRT conditions (D acc ≈ 180 nm, N acc ≈ 300 cm −3 ) is about 5× enhanced in comparison to the PR episodes. The Aitken mode (D Ait ≈ 80 nm, N Ait ≈ 120 cm −3 ) shows comparable absolute strength to that under PR conditions (see Table 2) but appears in the LRT N CN (D) distribution only as a shoulder. The N CCN (S,D) size distributions show that supersaturations S ≤ 0.3 % activate particles mostly in the accumulation mode range, whereas S > 0.3 % starts activating the Aitken mode population. The κ(S, D a ) size distribution shows κ Acc reaching rather high levels up to 0.40 (κ Acc = 0.35 ± 0.04) and κ Ait with values up to 0.2 (κ Ait = 0.18 ± 0.02). In comparison to the PR conditions, κ Acc was clearly enhanced due to the presence of aged, internally mixed, and salt-rich particles (see discussion in subsequent section). In contrast, the κ Ait levels were only slightly higher than during the PR periods, probably due to a broader accumulation mode base, which reached into the Aitken mode range. Note that the relative increase in κ(S, D a ) for the contrasting LRT and PR conditions is large enough to exert an influence on the CCN population, which is an exceptional case throughout the Amazonian seasons, since the κ(S, D a ) levels for most of the year vary within a rather narrow range (0.1 to 0.2) (see Part 1 paper).
The African LRT plumes that frequently impact the Amazon Basin during the wet season comprise a complex mixture of different aerosols components, including (i) a fraction of Saharan dust (mostly > 1 µm), (ii) biomass burning aerosols from fires in West Africa (mostly in the accumulation mode), and (iii) marine aerosols from the plume's transatlantic passage (in coarse and accumulation modes) (Andreae et al., 1986;Talbot et al., 1990;Swap et al., 1992;Weinzierl et al., 2017). Note that the African fires in West Africa are to a large extent agriculture-related and, thus, man-made (e.g., Barbosa et al., 1999;Capes et al., 2008). Fresh soot and uncoated dust particles typically have low hygroscopicities, whereas sea salt particles (i.e., NaCl and sulfates) represent comparatively efficient CCN. The LRT plumes make a rather long atmospheric journey -about 10 days according to Gläser et al. (2015) -which is associated with strong atmospheric processing and typically results in complex internally mixed particles (see Andreae et al., 1986). The resulting mixtures of dust and salt as well as coated soot particles, as commonly found in the dust plumes, readily act as CCN at realistic S levels (< 1 %) . Table 3 summarizes the ACSM results on aerosol chemical composition during LRT influence. 5 Note that the ACSM only measures the non-refractory fraction of the particle mass and, thus, does not detect a large fractions of the dust and salt constituents. During LRT conditions and with respect to the non-refractory part, organic mass dominated the particle composition (67 %), with minor nitrate contributions (3 %) and larger fractions of ammonium (11 %) and sulfate (9 %). Furthermore, a slight sea-salt-related increase in detected chloride mass (1 %) relative to the PR state was observed. Based on the ACSM results, a predicted κ p of 0.24 ± 0.01 was obtained, which agrees reasonably well with the measured hygroscopicity level, κ(0.11 %) = 0.35 ± 0.04. Accordingly, the observed elevated fractions of sulfate and ammonium were responsible for part of the increase in κ(S, D a ). The remaining difference between κ p and κ(0.11 %) can likely be explained by further refractory inorganics that were not covered by the ACSM. As an illustration of the complex mixing state of the African LRT aerosol population, Figs. S10 and S11 provide selected SEM-EDX data from a characteristic LRT aerosol sample. Note that these results merely serve as a qualitative example here, whereas a quantitative microspectroscopic analysis of LRT samples is the subject of ongoing work. The observed particles' morphology underlines the influence of atmospheric processing and shows a high degree of internal mixing. Chemically, the EDX maps show dust particles, sulfate salts, and a rather large abundance of NaCl particles. Figure 6d displays the characteristic CCN efficiency spectrum for the LRT conditions, which -expectedly -shows a rather steep increase at low S due to two effects pointing in the same direction: an enhanced accumulation mode and the presence of rather "good" CCN with comparatively high κ(S, D a ) levels. This large initial slope corresponds to a very small value for the characteristic variable S 1 = 0.09 %, which shows that, at comparatively low S (lowest S 1 among all analyzed conditions), 50 % of the aerosol population were al-5 ACSM data were available from August 2014 to September 2016. Accordingly, the ACSM time frame does not cover the highlighted LRT event, which is discussed in detail in this work. Instead, we analyzed the ACSM data for 12 comparable LRT episodes in 2015 and 2016 according to Moran-Zuloaga et al. (2017) (see also Table 1). ready activated as CCN (Table 4). At S levels around 0.3 %, ∼ 80 % of the aerosols acted as CCN; "full" activation (90 %) was reached at just S ≈ 0.5 %. At higher S (i.e., > 0.9 %) the efficiency spectrum approaches unity. This is in stark contrast to the PR CCN efficiency spectrum in Fig. 6b, where 50 % of the particles were activated at significantly higher S around 0.5 %, whereas full activation (90 %) was reached at high S around 1.5 %. Thus, the LRT episodes show a pronounced sensitivity to S only in the low-S regime, in contrast to the PR case with a sensitivity to S spanning across a wide S range. With the characteristic shape of the CCN efficiency spectrum (i.e., rather strong accumulation mode) and the rather low aerosol concentrations (N CN,10 ≈ 440 cm −3 , Table 4), the LRT conditions are located at the border between aerosol-limited and transitional regimes (compare Reutter et al., 2009;Pöschl et al., 2010).

Case study BB on aged biomass burning smoke
During the dry season, the ATTO site is frequently influenced by smoke from biomass burning (BB) activities in different regions of the Amazon forest (Freitas et al., 2005;Andreae et al., , 2015. As a characteristic example, the case study BB focuses on the strong biomass burning plume that was observed at the ATTO site in the middle of August 2014. During this event, pollution aerosol and trace gas concentrations reached their annual maxima, with N CN,10 peaking at 5000 cm −3 , c CO peaking at 350 ppb, and M BC e reaching up to 2.5 µg m −3 , as shown in Fig. 4. Selected meteorological, aerosol, and CCN time series of the event are shown in Fig. 8. This case study provides the opportunity to analyze the CCN properties of aged smoke from a rather defined large-scale BB plume in the Amazon region. Figure 8 shows that the influence of the BB smoke plume on the ATTO site lasted for about 6 days (18 to 22 August) with a gradual onset and decay. In terms of meteorology, this period was characterized by mostly cloud-free conditions (see SW in ) without precipitation, comparatively low RH levels, and some variability in wind direction. Note that, during the presence of this major smoke plume, atmospheric dimming in the ATTO region could be recognized (i.e., compare SW in maxima for the seven consecutive days).
The signature of the smoke aerosol particles can very clearly be seen in the dN/dlogD contour plot, N CN , as well as M BC e . In terms of particle size, the pronounced increase mostly occurred in the accumulation mode, which appears to be comparatively broad for this specific event. The CCN concentrations -e.g., N CCN (0.2 %) and N CCN (0.5 %) -track the relative increase in total aerosol abundance and show a 4-to 5-fold increase as well. At the same time, the presence of the pyrogenic aerosols correspond to a clear drop in aerosol hygroscopicity in both the Aitken ( κ Ait ≈ −0.05) and accumulation modes ( κ Acc ≈ −0.1), relative to the conditions before and after the major BB plume (see overlay of κ(S, D a ) size distributions and the dN/dlogD contour plot in Fig. 8d). This drop in κ(S, D a ) is associated with a high organic-tosulfate, OA / SO 2− 4 , ratio (Fig. 8f), reflecting the dominant role of organic constituents in biomass burning particles as documented in previous studies (Fuzzi et al., 2007;Lathem et al., 2013).
Geographically, the location of the fires and, thus, the origin of the strong biomass burning plume could be found by means of a combination of BTs and satellite data products as shown in Fig. S12 (Draxler and Hess, 1998;Acker and Leptoukh, 2007;Justice et al., 2011). The strong pollution at the ATTO site resulted from the presence of intense fires in the southern Amazon and a temporary "swing" of the BT track over the fire locations. During the dry season, the BTs mostly belong to the E and ESE clusters (see Figs. S1 and 4). For the period before and after the biomass burning plume, the BT track follows a "coastal path" and enters the continent in the region of the Amazon River delta (about 0 • N 50 • W). Subsequently, the air masses "follow" the Amazon River in westerly directions to the ATTO site. During the peak period of the BB event the BTs deviate from the coastal path and follow an "inland path" across the southeast of Brazil (see Figs. S12a and 4). At about 7 • S and 55 • W, the BTs intersect a region with strong fire activities, which are clearly visible in satellite products such as NO 2 total column measurements. These fires are localized along the Cuiabá-Santarém highway (BR-163). This highway corridor is known as a region of intense logging and burning of primary forest and its conversion to cattle pasture (Nepstad et al., 2002;Fearnside, 2007;. The transport time of the smoke from the fires to the ATTO site is about 2-3 days (given by the BTs), which provides a reference for the residence time and aging of the aerosol particles in the atmosphere. The satellite image in Fig. S12b shows the smoke plume that originated in the BR-163 region and traveled northwestwards. It clearly impacts the area around Manaus and the ATTO site precisely during the "event days" in August.
For a further characterization of the BB case study, we calculated a ratio of excess N CN,10 to excess c CO ( N CN,10 / c CO ) for the event of 17.9 ± 0.7 cm −3 ppb −1 (see Fig. S13a), which agrees well with the typical range for a variety of vegetation fires (30 ± 15 cm −3 ppb −1 ), in contrast to much higher N CN,10 / c CO levels for urban (100-300 cm −3 ppb −1 ) and power plant emissions (up to 900 cm −3 ppb −1 ) (Janhäll et al., 2010;Kuhn et al., 2010;. Furthermore, the ratios of excess N CCN (S) to excess c CO , N CCN (S) / c CO , for the individual S levels range between 6.7 ± 0.5 cm −3 ppb −1 for the lowest S = 0.11 % and values around 18.0 ± 1.3 cm −3 ppb −1 for higher S (see Table S4 and Fig. S13b). The N CCN (S)/ c CO ratios converge against N CN / c CO even for comparably small S (i.e., > 0.24 %), which can be explained by the fact that small S already activate a substantial fraction of the pronounced (mostly pyrogenic) accumulation mode (see discussion below). Kuhn et al. (2010) reported N CCN (0.6 %) / c CO ratios around 26 cm −3 ppb −1 for biomass burning plumes, which is consistent with our observations (i.e., N CCN (0.6 %) / c CO = 17.9 ± 1.3 cm −3 ppb −1 ; see Table S4). The obtained N CCN (S) / c CO ratios were utilized in a dedicated CCN parameterization scheme in our Part 1 study . Figure 6e summarizes the corresponding N CN and N CCN (S) size distributions as well as the size dependence of κ(S, D a ) for the BB case study. It shows a very strong accumulation mode (D acc ≈ 170 nm, N acc ≈ 3400 cm −3 ), "swamping" the Aitken mode (D Ait ≈ 70 nm, N Ait ≈ 140 cm −3 ) almost completely, giving the entire distribution a monomodal appearance. For S < 0.5 % almost the entire aerosol population is activated as CCN. The averaged κ(S, D a ) levels are rather low for both the Aitken and accumulation modes (κ Ait = 0.14 ± 0.01 and κ acc = 0.17 ± 0.02), in which κ acc is among the lowest values found in the accumulation mode size range throughout the entire study. The low κ(S, D a ) levels can be explained by the fact that pyrogenic aerosols predominantly contain organic constituents and rather low levels of inorganic species. The ACSM results during the BB period emphasize the predominant mass fraction of organics (87 %) as well as the minor contribution by nitrate (2 %), ammonium (3 %), and sulfate (4 %) ( Table 3). The predicted κ p of 0.15 ± 0.01 agrees reasonably well with the measurement result, κ(0.11 %) = 0.18 ± 0.01. Figure 6f displays the characteristic CCN efficiency spectrum for the BB period, which levels out clearly below unity. The dashed line shows the erf fit forced to go from 0 to 1 (i.e., with the pre-defined variable a 1 = 1), which does not match the data points for S > 0.5 %. This fit has been included here, since the activated fraction must reach 100 % eventually. For comparison, the solid line is an erf fit of the data where the plateau is an open fit parameter. This erf fit matches the data points very well, and the fit parameters as presented in Table 4 reveal the plateau at 93 %. Physically, this indicates the presence of an externally mixed aerosol population with 7 % of the particles being hydrophobic (e.g., a certain fraction of rather fresh soot) and not acting as CCN in the measured S range. The slope of the efficiency spectrum shows a steep increase for S < 0.4 %. According to these findings, the S-sensitive range is rather small with S < 0.4 %. According to Reutter et al. (2009), the BB case study conditions with the large number of available CCN (e.g., N CCN (0.47 %) > 4000 cm −3 ) fall into the updraft-limited regime.
It can be expected that the large aerosol load, its optical properties, and its ability to serve as CCN must already influence cloud properties and the stability of the thermodynamic profile of the atmosphere at both local and regional scales (Cecchini et al., 2017b). As mentioned above, the incoming solar radiation was dimmed compared to the days before and after this BB event. Furthermore, the cloud fraction decreased, which might result from stabilizing the atmosphere due to increased absorption of solar radiation in and above the boundary layer, the "semidirect effect" (e.g., Koren et al., 2004;Rosenfeld et al., 2008;Rosário et al., 2013). A detailed investigation of the direct radiative forcing and the modification of cloud properties by aerosol particles in the Amazon rain forest are clearly beyond the scope of this study. Nevertheless, the results shown here may serve as input for dedicated regional climate simulations.

Case study MPOL on the complex aerosol mixtures during the dry season
The previous BB case study presented the aerosol and CCN properties of a strong and well-defined regional biomass burning plume. However, the dry-season aerosol mixture at ATTO can be rather complex due to the influence of a variety of sources, such as biomass burning, fossil fuel combustion, and industrial emissions from local/regional sources as well as from African long-range transport, in addition to the natural aerosol background (i.e., PBAP, SOA, marine aerosols) (e.g., Freud et al., 2008;Artaxo et al., 2013;Saturno et al., 2017a;. Accordingly, the dry-season aerosol mixture is highly variable and no single episode reflects the conditions comprehensively. Therefore, we defined a mixed pollution (MPOL) case study, which is evidently influenced by local/regional biomass burning in South America and the long-range transport of African aerosols. The MPOL case serves as an example of the highly variable aerosol conditions during the Amazonian dry season. The 7-day MPOL period in September 2014 shows an exceptionally low OA / SO 2− 4 mass ratio (Table 3). Saturno et al. (2017b) recently showed that the high sulfate concentrations can be explained by the long-range transport of volcanogenic aerosols from Africa (i.e., from the Nyiragongo and Nyamuragira volcanoes in eastern Congo) into the Amazon (compare also Fioletov et al., 2016). While the volcanogenic aerosol shows characteristic properties that allow this LRT component to be distinguished from the local/regional BB aerosol, African BB aerosols can be transported similarly; however, an experimental discrimination of African vs. Amazonian BB aerosol is difficult (see Saturno et al., 2017a). Upon arrival of the African plume in the Amazonian atmosphere, the LRT aerosol has mixed with local/regional fires emissions.
Meteorologically, the time frame of the MPOL period was mostly cloud-free (see daily profile in SW in ) and without precipitation (see P TRMM and P ATTO ), as well as characterized by rather stable wind conditions (Fig. 9). With respect to the aerosol and CCN parameters, the relevant time seriessuch as N CN , M BC e , and N CCN (S) -show a high variability. Specifically, the dN /dlogD contour plot shows an alternating pattern: on one hand, and marked by a grey shading, rather extended periods with comparably low aerosol concentrations (around 1000 cm −3 ) and high κ(S, D a ) values (up to 0.35) can be observed. The κ(S, D a ) levels reaching ∼ 0.35 are among the highest in the entire dry season of 2014 (compare Fig. 4). On the other hand, and marked by a light purple shading, these conditions are interrupted by several pulses with strongly enhanced aerosol concentrations (up to 5000 cm −3 ) as well as substantially lower κ(S, D a ) values (around 0.1). The changes in κ(S, D a ) occur with simultaneous changes in the aerosol chemical composition: slight increases of the OA / SO 2− 4 ratio indicate that the pulses comprise organic-rich aerosol due to the influence of local/regional BB plumes, whereas the lower OA / SO 2− 4 aerosol is comparatively rich in sulfate due to the volcanogenic origin.
A combination of BTs and satellite data during the MPOL period shows that all BTs follow an easterly direction along the Amazon River (Fig. S14), which is the most frequent scenario during the dry season (see C. . The same study also shows that during this period the shores of the Amazon River can be regarded as the core region of the ATTO site footprint, where BT densities are highest. Accordingly, all aerosol and trace gas sources in these areas are of primary importance for the ATTO region. For instance, this is true for a deforestation hot spot in the area around the cities Oriximina and Òbidos as well as a variety of anthropogenic sources (i.e., industry, power plants, cities, shipping) (compare Fig. S14 and C. . During the MPOL time frame, several (smaller) deforestation fires were observed within the fetch of the corresponding BTs (Fig. S14). These fires, which mostly burnt for less than a day according to satellite observation, are likely responsible for the low-κ(S, D a ) and high-OA / SO 2− 4 pulses within the MPOL period. Thus, the pulses can be considered as the advection of nearby biomass burning plumes into the ATTO region. According to the BT data, the smoke experienced a transport and aging time of 12-18 h. Thus, the smoke plumes during MPOL are fresher than during the BB case study, which experienced atmospheric aging for 2-3 days. This difference in aging might be related to differences in the corresponding κ(S, D a ) values, with fresh smoke during MPOL showing a lower hygroscopicity (κ <100 nm,MPOL ≈ 0.10) and the aged smoke showing higher values (κ Ait,BB ≈ 0.14, κ acc,BB ≈ 0.17). Note that biomass burning smoke cannot explain the sulfate-rich aerosol during MPOL since BB-related sulfate contents are typically below 6-7 % (e.g., compare BB case in Table 3 as well as Fuzzi et al., 2007;Gunthe et al., 2009;Saturno et al., 2017b). Figure 6g and h summarize the N CN (D), N CCN (S,D), and κ(S, D a ) size distributions during MPOL, separately for the biomass burning pulses (MPOL-BB with OA / SO 2− 4 ≈ 4) and LRT influence (MPOL-LRT with lower OA / SO 2− 4 ≈ 3). In both cases, the size distributions show a broad monomodal distribution, which did not allow a stable double lognormal mode fitting of Aitken and accumulation modes (see Table 4). The mode is centered at ∼ 135 nm for MPOL-LRT, whereas the relatively fresh biomass burning smoke during MPOL-BB shows a modal diameter of ∼ 113 nm, in agreement with ∼ 100 nm for fresh biomass burning smoke reported by Andreae et al. (2004). The corresponding N CCN (S,D) size distributions show similar shapes, albeit with substantial absolute differences in CCN concentrations. Furthermore, clear differences are also observed for the average κ(S, D a ) size distributions: during MPOL-LRT, κ(S, D a ) shows a pronounced size dependence. The average κ for sizes < 100 nm is rather size independent (κ < 100 nm = 0.14 ± 0.01). Instead, the av-erage κ > 100 nm increases with D up to 0.26 (on average: κ > 100 nm = 0.22 ± 0.03). According to the shape of the κ(S, D a ) size distribution in Fig. 6g, it can be assumed that the aerosol hygroscopicity was even higher for D larger than the covered size range here (i.e., > 170 nm). During the dry season, the highest κ(S, D a ) levels for accumulation mode particles were observed during the peak abundance of sulfate at the ATTO site. The hygroscopicity during the MPOL-BB pulses shows generally lower values and weaker size dependence for particles < 150 nm. The average κ < 150 nm = 0.10 ± 0.01 was even smaller than during BB and PR conditions and represents one of the lowest values measured during the entire observation period. For larger particles (e.g., > 150 nm), κ(S, D a ) strongly increased towards values comparable to those during MPOL-LRT, showing that both conditions are superimposed (on average: κ > 150 nm = 0.20 ± 0.04). Figure 6i shows the CCN efficiency spectra for the two MPOL states. The slope of the MPOL-LRT spectrum is significantly steeper than the slope of the MPOL-BB spectrum. The S 1 level of 50 % activation for the sulfate-rich aerosol population (0.16 %) is clearly lower than during the short biomass burning pulses (0.28 %). This rather large difference can be explained by the smaller modal diameter of the MPOL-BB relative to the MPOL-LRT case. Furthermore, κ is significantly decreased for the biomass burning pulses, which are dominated by organic constituents. However, note that the absolute CCN concentration is -while being less hygroscopic -significantly higher for MPOL-BB periods.
In general, the MPOL case study emphasizes the following aspects: (i) the dry-season aerosols that arrive at the ATTO site can be rather complex mixtures of superimposed emissions from different sources with contrasting chemical properties. (ii) The properties of the aerosol and CCN population can change rather suddenly and substantially (see N CN and N CCN (S) changes by a factor of 3-4 within a few hours). Similarly, the aerosol hygroscopicity can vary quite strongly from the lowest value observed in the entire study (∼ 0.1) to values around 0.35 and higher, which are among to the largest values observed here during the dry season. These quickly and substantially changing aerosol regimes will presumably also impact the cloud conditions during the dry season. (iii) Finally, the Amazonian aerosol and CCN population can be substantially perturbed by emissions from sources (e.g., volcanoes in eastern Congo) that are remarkably far away from the ATTO site (∼ 10 000 km) (Saturno et al., 2017b). This emphasizes very clearly that intercontinental influences have to be considered carefully in the analysis of the Amazonian atmospheric composition.

Aerosol particle hygroscopicity distributions and aerosol mixing state
In this section, we investigate the aerosol particle mixing state for the different case study conditions with the help of the aerosol particle hygroscopicity distribution -or κ dis- Figure 10. Average probability distribution of particle hygroscopicity, dH /dlogκ, on the left side and the same quantity weighted by the particle number size distribution, (dH · dN )/(dlogκ · dlogD), on the right side, plotted over the effective hygroscopicity parameter, κ, and dry-particle diameter, D, for (a and b) the entire measurement period as well as (c and d) PR, (e and f) LRT, (g and h) BB, (i and j) MPOL-LRT, and (k and l) MPOL-BB conditions. The particle size distributions used for the weighting are shown in Fig. 6. tribution -concept introduced by Su et al. (2010). This approach visualizes the spread of κ values among particles of a given size. Specifically, in an ideal internal particle mixture, all particles have the same chemical composition and therefore the same hygroscopicity, resulting in a narrow and defined κ distribution. In an external mixture, the particles at a given size can have widely different chemical compositions and hygroscopicities, resulting in a broad κ distribution. Figure 10 summarizes two versions of κ distributions for the contrasting case study conditions: (i) the "classical" κ distributions according to Su et al. (2010), which emphasize the spread of κ levels for all particle diameters across the measured size range, and (ii) κ distributions weighted with the corresponding average particle size distributions from Fig. 6, which provide a quantitative overview of particle abundance as a function of hygroscopicity and size (N CN κ distribution). The comparison of the κ and N CN κ distributions for the contrasting case study conditions emphasizes similarities and differences between the corresponding aerosol populations, which allows drawing conclusions on the aerosol mixing state and microphysical properties.
The κ distributions for most conditions reflect a bimodal character of the corresponding aerosol distributions with distinctly different properties in the Aitken and accumulation modes as outlined in Fig. 6. Specifically, all distributions show an increasing spread of κ levels towards larger particle diameters, which suggests a higher degree of external particle mixing and therefore a higher diversity of particle properties (i.e., hygroscopicity) in the accumulation than in the Aitken mode. As an example, the BB and MPOL-BB cases show a κ spread in the accumulation mode range that reaches from values well below 0.1 up to levels of about 1. Remarkably, the PR κ distribution differs from all other cases since it shows overall the smallest spread of κ over the entire size range. This suggests the Aitken and accumulation mode particles under PR conditions are two distinct and chemically rather homogeneous aerosol populations with a comparatively high degree of internal mixing. As an example, the PR Aitken mode particle population covers a defined κ range between ∼ 0.1 and ∼ 0.15. In contrast, the LRT, BB, and MPOL aerosol populations appear to be more externally mixed.
In addition to the diversity of the hygroscopicity as visible in the κ distributions, the N CN κ distributions further emphasize the quantitative abundance of particles in the hygroscopicity-size space. Accordingly, the N CN κ distributions can be regarded as signature-like representations of the aerosol microphysical state under certain conditions. Note that the N CN κ distributions in Fig. 10 differ substantially from each other. The PR case shows a unique signature. The LRT and MPOL-LRT cases show certain similarities due to the fact that both are characterized by similar aerosol size distributions and comparatively high κ levels. The comparison of the relatively fresh MPOL-BB smoke and the relatively aged BB smoke emphasizes the aging-related increases in particle size and hygroscopicity by means of a characteristic shift of the dominant mode in the N CN κ distributions. In both cases the spread of κ is rather large, indicating a comparatively strong external mixing in the smoke plumes. In essence, the κ distributions and N CN κ distributions are valuable overview representations, which combine characteristic aerosol properties in terms of particle size, particle concentration, κ diversity, and the aerosol mixing state in a fingerprint-like manner. So far, only very few studies (e.g., Mahish et al., 2018) have used the κ distribution or related concepts to characterize ambient aerosol properties. In light of the results in Fig. 10, we suggest that this concept should be used more broadly as it provides valuable insights into the particle mixing state beyond the more established characterizations of aerosol and CCN properties.
3.9 Overview of CCN efficiency spectra and corresponding CCN spectra CCN efficiency spectra serve as normalized CCN signatures. Their shape is influenced by (i) the shape of the N CN size distribution (i.e., relative strength of Aitken vs. accumulation modes), (ii) the aerosol composition through the κ(S, D a ) values and its size dependence, and (iii) the mixing state of the aerosol as represented in the κ and N CN κ distributions. CCN spectra provide quantitative information on the actual CCN concentrations as a function of S. From the CCN efficiency spectra, CCN spectra are readily obtained by multi-plication with the corresponding average N CN concentrations (Table 4). This last section combines the CCN efficiency spectra (i.e., the erf fits) and CCN spectra of all analyzed case study conditions from this work with the seasonally averaged spectra from the Part 1 study and literature data. Figure 11 shows an overview of all spectra. The direct comparison emphasizes characteristic similarities and differences as a basis for a concluding discussion on aerosol-cloud interactions. Note in this context that Farmer et al. (2015) presented "cumulative numbers of CCN, normalized to CN", which is conceptually related to the CCN efficiency spectra reported here. Accordingly, a comparison of the spectra reported by Farmer et al. (2015) with Fig. 11 may help to put the characteristics of the Amazonian CCN population into a broader context. The peak supersaturation and its variability are an essential parameter to understand aerosol-cloud interactions. However, only sparse quantitative information on the actually relevant S range is available. The spectra in Fig. 11 are plotted for a broad S range from 0.001 to 20 %. According to Reutter et al. (2009), this range can be generally subdivided into very low (S < 0.1 %), low (S < 0.2 %), transitional (0.2 % < S < 0.5 %), and high (S > 0.5 %) supersaturation regimes. Furthermore, a recent study by Fan et al. (2018) suggests that under certain conditions even very high supersaturations (S 1 %) can be reached in deep convective clouds. One approach to actually quantify ATTOrelevant average peak S at cloud base, S cloud (D H ,κ), uses the position of the Hoppel minimum, D H , as outlined in Hoppel et al. (1986) and Krüger et al. (2014). According to results in our Part 1 companion paper and the present study (see Table 2), ATTO-relevant S cloud (D H ,κ) values range from ∼ 0.15 to ∼ 0.34 %. This S cloud (D H ,κ) range is shown as a "S landmark" in Fig. 11 for orientation.
The array of condition-specific CCN efficiency spectra in Fig. 11a shows the diversity of spectral shapes. The PRspecific spectrum represents the lower limiting case with the "slowest" increase in activated fraction upon increasing S (e.g., 50 % activation reached at S ≈ 0.5 %), whereas the BB and LRT spectra represent the upper limiting cases, reaching high activated fractions at relatively low S (50 % activation at S ≈ 0.15 % for the BB case and at S ≈ 0.1 % for the LRT case). The slopes of the spectra, d(N CCN (S)/N CN,10 )/dS, indicate how sensitively the activated fractions react towards changes in supersaturation, S. Overall, the highest sensitivities towards S occur between ∼ 0.1 and ∼ 1.0 %. However, the cases have to be investigated individually to obtain condition-specific "high-sensitivity regimes". For low S (< 0.1 %) -corresponding to the activation of accumulation and coarse-mode particles -the aerosol populations that act as CCN most efficiently are those with strong accumulation modes and high κ levels, such as the sea-salt-rich LRT and sulfate-rich MPOL-LRT populations. In contrast, the PR aerosol acts as CCN least efficiently as it is characterized by a small fraction of accumulation mode particles with rather Figure 11. Overview and comparison of normalized CCN efficiency spectra and number-concentration-based CCN spectra for characteristic conditions and seasons. (a and b) PR, LRT, BB, MPOL-LRT, and MPOL-BB conditions as defined in this paper. (c and d) Seasonally averaged spectra from the Part 1 companion paper , CCN efficiency spectrum from Roberts et al. (2001), and CCN spectra from Roberts et al. (2003) and Gunthe et al. (2009). (e and f) Conditions representing different aging states of biomass burning aerosols based on BB and MPOL-BB conditions from present work and data from a previous study by Andreae et al. (2004). For clarity the erf fit with the pre-defined variable a 1 = 1 was used for the BB case (compare Fig. 6f). CCN spectra in (b) were obtained from multiplication of CCN efficiency spectra in (a) with corresponding average aerosol number concentrations in Table 4. Markers represent measured average CCN concentrations for case study periods. Error bars at markers represent 1 SD. Good agreement of CCN spectra and markers underlines reliability of CCN efficiency spectra in representation of CCN population. Blue vertical shading represents estimated peak supersaturations at cloud base, S cloud (D H ,κ), in the ATTO region according to Pöhlker et al. (2016) and the present study. The colors were chosen according to Wong (2011). low κ. In the transitional S regime with 0.2 % < S < 0.5 % -corresponding to the activation of particles between the Aitken and accumulation modes (i.e., the Hoppel minimum size range) -the individual spectra show their highest divergence and thus the largest differences in CCN efficiency. Note that this range is collocated with the experimentally de-duced and ATTO-relevant S cloud (D H ,κ) levels. For high S (> 1 %) -corresponding to the activation of Aitken mode and even smaller particles -full activation is reached and sensitivities towards S decrease.
For comparison, the season-specific CCN efficiency spectra from our Part 1 study are shown in Fig. 11c. Generally, the shapes of the condition-specific spectra and the seasonspecific spectra agree well (e.g., relationship between wet and dust seasons and between PR and LRT conditions). However, the characteristic spectral features are more pronounced for the conditions than for the seasons, due to the fact that the case studies on certain conditions incorporate more defined aerosol plumes and/or populations. As an example, the LRT season spectrum includes several LRT events, as well as clean periods in between, whereas the LRT case study spectrum includes only the core period of one defined LRT episode (see Table 1).
Since the size and composition of aerosol particles change dynamically due to atmospheric aging and processing, the CCN efficiency spectra also change accordingly. Figure 11e emphasizes the dynamic character of the shape of the CCN efficiency spectra by means of different aging states of biomass burning plumes. Here we combined four biomassburning-related CCN efficiency spectra: (i) the BB case study spectrum from this work, which represents smoke after ∼ 2-3 days of atmospheric aging; (ii) the MPOL-BB case study spectrum from this work, which represents smoke after ∼ 1 day of aging; (iii) "cloud-processed smoke" from biomass burning regions in southeast Brazil after hours to days of atmospheric aging according to Andreae et al. (2004); and (iv) "fresh smoke in the mixed layer", also from southeastern Brazil, which was sampled in the fire plumes and thus was aged for minutes to hours only (also from Andreae et al., 2004). The spectral shapes in Fig. 11e clearly differ: the lowest activated fractions were observed for the fresh smoke (50 % activation at S ≈ 1.0 %; 90 % at S ≈ 4.0 %), followed by the cloud-processed smoke (50 % activation at S ≈ 0.5 %; 90 % at S ≈ 2.0 %), then the MPOL-BB spectrum (50 % activation at S ≈ 0.3 %; 90 % at S ≈ 1.2 %), and finally the BB spectrum (50 % activation at S ≈ 0.2 %; 90 % at S ≈ 0.4 %) with the highest activated fractions as the upper limiting case. Atmospheric aging tends to increase the particle size through coagulation and condensational growth, and to enhance the particle hygroscopicity through oxidation, aqueous-phase chemistry, and reaction product deposition. Therefore, aging tends to increase the strength of the accumulation at the expense of the Aitken mode and increases κ. Accordingly, it evolves the smoke's CCN efficiency spectra from the "fresh-smoke" conditions -as the initial state -towards the BB case study conditions and presumably even further. This underlines the well-known trend that atmospheric aging increases the suitability of a given particle population to act as CCN . Important to note in the context of this study is the following: the CCN efficiency spectra represent signatures of a given aerosol population in a given state of atmospheric aging. Accordingly, the atmospheric aerosol aging and the dynamic evolution of the CCN efficiency spectra's shape have to be kept in mind during discussion and utilization of the spectra in follow-up studies.
From all CCN efficiency spectra the corresponding CCN spectra were calculated as displayed in Fig. 11b, d, and f. Moreover, measured CCN spectra from previous, mostly short-term, campaigns in the Amazon Basin are also shown and agree well with our results (Roberts et al., 2001(Roberts et al., , 2003Andreae et al., 2004;Gunthe et al., 2009). Beyond the literature data shown in Fig. 11, good agreement was further observed with Andreae (2009) and Martins et al. (2009). Overall, Fig. 11 may serve as a basis for dedicated cloud microphysical studies on the characteristic differences between the aerosol/CCN populations and their impacts on cloud properties. Particularly, the results obtained here (i.e., N CN concentrations and CCN efficiency spectra) can be used to investigate the sensitivity of clouds under PR conditions, as an approximation for pristine atmospheric conditions in tropical continental regions. The large differences between PR background conditions and perturbed atmospheric states related to anthropogenic (aged) BB smoke in terms of total aerosol concentration as well as the shape of the CCN efficiency spectra are evident. Similarly, the differences between the PR and LRT case studies suggest that the frequent LRT events in the wet season are related to simultaneous changes in the cloud microphysical state, although the changes in total aerosol concentration are comparatively small.

Summary and conclusions
In a recent synthesis paper on aerosol-cloud interactions and their highly uncertain representation in global climate models, Seinfeld et al. (2016) proposed that long-term and focused observations in "geographic areas that are critical in climate response" are necessary to obtain a detailed process understanding. Further, studies in "those regions of the present-day atmosphere that approximate preindustrial conditions" will help to "replicate preindustrial aerosol-cloud relationships". In these regions -such as the Amazon Basin -clouds are particularly sensitive to small changes in CCN concentrations (Carslaw et al., 2013). Accordingly, observations are needed here to obtain crucial knowledge on the man-made perturbation of preindustrial aerosol-cloud interactions. This work aims to help tackle this major scientific challenge by presenting detailed long-term aerosol and CCN data for characteristic atmospheric states at the Amazon Tall Tower Observatory (ATTO) in the central Amazon Basin, which is a unique, climate-relevant location with atmospheric conditions oscillation between pristine and anthropogenically strongly perturbed states.
The basis for this work is size-resolved measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations and hygroscopicity at ATTO over a full seasonal cycle (March 2014-February 2015. The results of these observations are presented in two papers: the recently published Part 1 paper provides an in-depth analyses of the multi-month patterns in the Amazonian CCN population as well as seasonal averages of the key CCN parameters . Further, Part 1 compares and discusses different CCN parametrization schemes and their suitability to represent the Amazonian CCN cycling in modeling studies. The present Part 2 study completes this picture by analyzing the CCN variability at the original time resolution (4.5 h), which is sufficient to resolve its short-term variability in relation to air mass changes as well as aerosol emission and transformation processes.
A focal point of both studies is the concept of CCN efficiency spectra, which represent a tool to visualize the different behaviors of contrasting aerosol populations in cloud formations and, thus, can be regarded as "CCN signatures". Analytically, the CCN efficiency spectra can be described precisely and in a physically correct way by Gaussian single-or double-error-function (erf) fits. In contrast to other common analytical functions, the erf approach describes the measurement results very accurately and allows CCN properties to be extrapolated to experimentally hardly accessible supersaturations in the low-and high-S regimes.
Here, we zoom into the long-term CCN data in two steps: first, we discuss the aerosol and CCN variability for two 2-month periods that represent contrasting regimes in the aerosol, cloud microphysical, and precipitation seasonality in the central Amazon. The selected periods provide insights into the characteristic atmospheric cycling during the clean wet season and the polluted dry season. Second, we focus on the following four selected case study periods, which represent particularly relevant atmospheric states: Empirically pristine rain forest (PR) conditions are one of the scientifically most relevant atmospheric states at ATTO. Here, we defined PR conditions by means of black carbon and CO concentrations as pollution tracers. At ATTO, the PR frequency of occurrence peaks between the second half of April and the first half of May. Under PR conditions, aerosol concentrations are very low (∼ 290 cm −3 ), and the aerosol population has a characteristic bimodal shape with a dominant Aitken and comparatively weak accumulation mode (D Ait ≈ 70 nm; N Ait ≈ 160 cm −3 vs. D acc ≈ 160 nm; N acc ≈ 90 cm −3 ). The aerosol particles are composed of mostly organic matter with minor amounts of inorganic constituents (OA: 0.64, NO − 3 : 0.03, SO 2− 4 : 0.04, Cl − : < 0.01, BC e : < 0.01 µg m −3 ). The observed low κ(S, D a ) levels agree with the particles' composition and show a size dependence (κ Ait = 0.12 ± 0.01 vs. κ acc = 0.18 ± 0.01). The CCN efficiency spectrum shows a characteristic shape since it converges towards full activation rather slowly (50 % activation at ∼ 0.5 %, 90 % activation at ∼ 1.5 %). Thus, the CCN population is sensitive towards S in both the low-and high-S regime. Accordingly, the CCN population can be regarded as both aerosol-sensitive due to the low total aerosol concentrations and updraft-sensitive according to the CCN efficiency spectrum with its sensitivity to S across a wide S range.
During long-range-transport (LRT) episodes within the wet season, major amounts of aged North African dust, West African biomass burning smoke, and Atlantic marine aerosols are advected on an event basis into the basin (mostly February-April). Total aerosol concentrations (∼ 440 cm −3 ) are slightly enhanced relative to the PR state, and the aerosol population has a bimodal shape with a minor Aitken and a stronger accumulation mode (D Ait ≈ 80 nm, N Ait ≈ 120 cm −3 vs. D acc ≈ 180 nm, N acc ≈ 300 cm −3 ). Besides the non-refractory fraction of organics and inorganics (OA: 1.81 µg m −3 ; NO − 3 : 0.08; NH + 4 : 0.30; SO 2− 4 : 0.25; Cl − : 0.04; BC e : 0.21 µg m −3 ), a larger refractory fraction of mineral dust and sea salts can be found in internally mixed particles. The observed κ(S, D a ) levels are increased compared to the PR state in agreement with the chemical composition (κ Ait = 0.18 ± 0.02 vs. κ acc = 0.35 ± 0.04). The CCN efficiency spectrum shows a steep increase -and thus high sensitivity to S -at low S and quickly converges against full activation towards high S (50 % activation at ∼ 0.09 %, 90 % activation at ∼ 0.53 %). Thus, the CCN regime under LRT influence is at the border of the aerosol-limited and transitional regimes.
The corresponding CCN efficiency spectrum shows a rather steep increase at low S and converges against a threshold (∼ 93 %) below full activation at high S (50 % activation at S ≈ 0.15 %). With respect to the large particle concentrations and the large sensitivity of the CCN efficiency spectrum to S in the low-S regime, the BB case falls into the updraftlimited regime.
During the dry season, the central Amazon often experiences mixed aerosol populations from regional, continental, and even transcontinental sources. Here, we analyzed one characteristic example of such mixed-pollution (MPOL) scenarios, in which a mixture of African volcanogenic emissions and nearby Amazonian fires impacted the ATTO site: under conditions with a predominant influence of the African volcanogenic emissions, we found a broad monomodal size distribution (D mode ≈ 130 nm, N mode ≈ 1300 cm −3 ), strongly enhanced sulfate levels (OA: 5.50; SO 2− 4 : 1.75 µg m −3 ), and correspondingly elevated hygroscopicities (κ < 100 nm = 0.14 ± 0.01 vs. κ > 100 nm = 0.22 ± 0.03). Under conditions with predominant influence by the nearby fires, we found high concentrations in a monomodal distribution (D mode ≈ 110 nm, N mode ≈ 2800 cm −3 ), an enhancement of organic matter on top of the sulfate background (OA: 7.88; SO 2− 4 : 2.03 µg m −3 ), and low hygroscopicities (κ < 150 nm = 0.10 ± 0.01 vs. κ > 150 nm = 0.20 ± 0.04). Accordingly, the interplay of the aged volcanogenic plume and the fresh smoke resulted in large variations of the total aerosol concentration, aerosol composition, and CCN properties. We suppose that the highly variable CCN population results in associated (microphysical) variations in cloud properties.
Hygroscopicity distributions were analyzed for all conditions, providing detailed and characteristic insights into the mixing state of the different types of aerosols. We found that the spread of κ increases with size for all conditions. The κ distributions suggest that the PR aerosol population is rather internally mixed, whereas the BB, LRT, and MPOL aerosols show more external mixing states. In essence, the κ distributions and N CN κ distributions are valuable overview representations, combining characteristic aerosol properties in terms of particle size, particle concentration, κ levels, and aerosol mixing state in a fingerprint-like manner. This representation helps to further elucidate aerosol-cloud interactions, such as the shapes of the CCN efficiency spectra: as general tendencies, more externally mixed aerosols, resulting in broader κ distributions, also broaden the CCN efficiency spectra -analogous to broad N CN distributions. Internally mixed aerosols with more defined κ distributions tend towards steeper segments in the CCN efficiency spectra. Furthermore, externally mixed aerosols with distinctly different κ levels tend to introduce further steps/plateaus into the CCN efficiency spectra, in addition to plateaus caused by multimodal N CN distributions. However, the CCN efficiency spectra for the conditions reported here are primarily shaped by the particle size distributions and average κ levels, whereas the diversity of κ seems to play a minor role. To clarify exactly how the signatures and patterns in κ and N CN κ distributions are related to the signatures and shapes of the CCN efficiency spectra, dedicated future studies at contrasting locations and modeling support are required.
Finally, the CCN efficiency spectra and CCN spectra for all analyzed cases are discussed in an overview, which emphasizes the following observations: (i) the combination of CCN efficiency spectra for all analyzed conditions show a large variability. (ii) Within this range, the estimated peak supersaturations at cloud base, S cloud (D H ,κ), are collocated with the intermediate S range, in which the CCN efficiency spectra show their highest variability, thus underlining the impact of changing aerosol populations on cloud properties. (iii) The sensitivity of the CCN populations to changes in S is conditions-specific with highest susceptibilities towards S between S = 0.1 and S = 1 %. (iv) The combination of CCN efficiency spectra for different, particularly contrasting, aerosol populations provides a basis for follow-up studies on the aerosol-related differences in cloud properties in the Amazon region and beyond. (v) Finally, the atmospheric aging of aerosol particles in the atmosphere is reflected in a corresponding evolution of the shape of the CCN efficiency spectra and has to be kept in mind upon their utilization. All numbers are given as mean and 1 SD. The time series of the CCN key parameters for the entire measurement period can be found in the Supplement of the Part 1 paper . For data requests beyond the available data, please refer to the corresponding authors.
Appendix A: List of frequently used symbols.

Symbol
Quantity and unit a mode (mode = 1, 2) Prefactor of single-and double-erf fits CCN number concentration at a certain S, cm −3 N CCN (S, D) CCN number concentration at a certain S and D, cm −3 N CCN (S)/N CN,10 CCN efficiency N CN,Dcut CN number concentration (> D cut ), cm −3 N CN,10 CN number concentration (> 10 nm), cm −3 N CN,Acc Accumulation mode particle number concentration, cm −3 N CN,Ait Aitken mode particle number concentration, cm −3 N d Cloud droplet number concentration, cm −3 N db Cloud droplet number concentration at cloud base, cm −3 P ATTO Precipitation rate at ATTO, mm h −1 P BT Cumulative precipitation from HYSPLIT BTs, mm P TRMM Precipitation from TRMM satellite mission, mm h −1 r e Cloud droplet effective radius, µm S Water vapor supersaturation, % S cloud (D H ,κ) Average peak supersaturation in cloud, % S mode (mode = 1, 2) Midpoint activation supersaturation from CCN efficiency spectra, % SW in Incoming shortwave radiation (285 to 2800 nm), W m −2 θ e Equivalent potential temperature, K U Wind speed, m s −1 w b Updraft velocity at cloud base, m s −1 w mode (mode = 1, 2) Width of CCN efficiency spectra σ Width of lognormal fit in Aitken and accumulation mode fitting