Size-resolved long-term measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations and hygroscopicity were conducted at the remote Amazon Tall Tower Observatory (ATTO) in the central Amazon Basin over a 1-year period and full seasonal cycle (March 2014–February 2015). The measurements provide a climatology of CCN properties characteristic of a remote central Amazonian rain forest site. The CCN measurements were continuously cycled through 10 levels of supersaturation (S = 0.11 to 1.10 %) and span the aerosol particle size range from 20 to 245 nm. The mean critical diameters of CCN activation range from 43 nm at S = 1.10 % to 172 nm at S = 0.11 %. The particle hygroscopicity exhibits a pronounced size dependence with lower values for the Aitken mode (κ_Ait = 0.14 ± 0.03), higher values for the accumulation mode (κ_Acc = 0.22 ± 0.05), and an overall mean value of κ_mean = 0.17 ± 0.06, consistent with high fractions of organic aerosol. The hygroscopicity parameter, κ, exhibits remarkably little temporal variability: no pronounced diurnal cycles, only weak seasonal trends, and few short-term variations during long-range transport events. In contrast, the CCN number concentrations exhibit a pronounced seasonal cycle, tracking the pollution-related seasonality in total aerosol concentration. We find that the variability in the CCN concentrations in the central Amazon is mostly driven by aerosol particle number concentration and size distribution, while variations in aerosol hygroscopicity and chemical composition matter only during a few episodes. For modeling purposes, we compare different approaches of predicting CCN number concentration and present a novel parametrization, which allows accurate CCN predictions based on a small set of input data.

Around 50% of humankind relies on groundwater as a source of drinking water. Here we investigate the age, geochemistry, and microbiology of 138 groundwater samples from 95 monitoring wells (<250 m depth) located in 14 aquifers in Canada. The geochemistry and microbiology show consistent trends suggesting large-scale aerobic and anaerobic hydrogen, methane, nitrogen, and sulfur cycling carried out by diverse microbial communities. Older groundwaters, especially in aquifers with organic carbon-rich strata, contain on average more cells (up to 1.4 × 10⁷ mL⁻¹) than younger groundwaters, challenging current estimates of subsurface cell abundances. We observe substantial concentrations of dissolved oxygen (0.52 ± 0.12 mg L⁻¹ [mean ± SE]; n = 57) in older groundwaters that seem to support aerobic metabolisms in subsurface ecosystems at an unprecedented scale. Metagenomics, oxygen isotope analyses and mixing models indicate that dark oxygen is produced in situ via microbial dismutation. We show that ancient groundwaters sustain productive communities and highlight an overlooked oxygen source in present and past subsurface ecosystems of Earth.

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. Biomass burning (BB) conditions characteristic for the Amazonian dry season from August to November. The BB episodes show a very strong accumulation mode (D_Ait ≈ 70 nm, N_Ait ≈ 140 cm⁻³ vs. D_acc ≈ 170 nm, N_acc ≈ 3400 cm⁻³), very high organic mass fractions ( ∼ 90 %), and correspondingly low hygroscopicity (κ_Ait ≈ 0.14, κ_acc ≈ 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, N_CN, 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, N_CN, 10 ≈ 2800 cm⁻³) with an organic-dominated 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.

The Amazon rainforest is a sensitive ecosystem experiencing the combined pressures of progressing deforestation and climate change. Its atmospheric conditions oscillate between biogenic and biomass burning (BB) dominated states. The Amazon further represents one of the few remaining continental places where the atmosphere approaches pristine conditions during occasional wet season episodes. The Amazon Tall Tower Observatory (ATTO) has been established in central Amazonia to investigate the complex interactions between the rainforest ecosystem and the atmosphere. Physical and chemical aerosol properties have been analyzed continuously since 2012. This paper provides an in-depth analysis of the aerosol's optical properties at ATTO based on data from 2012 to 2017. The following key results have been obtained. The aerosol scattering and absorption coefficients at 637 nm, σ_sp,637 and σ_ap,637, show a pronounced seasonality with lowest values in the clean wet season (mean ± SD: σ_sp,637 = 7.5±9.3 M m⁻¹; σ_ap,637 = 0.68±0.91 M m⁻¹) and highest values in the BB-polluted dry season (σ_sp,637 = 33±25 M m⁻¹; σ_ap,637 = 4.0±2.2 M m⁻¹). The single scattering albedo at 637 nm, ω₀, is lowest during the dry season (ω₀ = 0.87±0.03) and highest during the wet season (ω₀ = 0.93±0.04). The retrieved BC mass absorption cross sections, α_abs, are substantially higher than values widely used in the literature (i.e., 6.6 m² g⁻¹ at 637 nm wavelength), likely related to thick organic or inorganic coatings on the BC cores. Wet season values of α_abs = 11.4±1.2 m² g⁻¹ (637 nm) and dry season values of α_abs = 12.3±1.3 m² g⁻¹ (637 nm) were obtained. The BB aerosol during the dry season is a mixture of rather fresh smoke from local fires, somewhat aged smoke from regional fires, and strongly aged smoke from African fires. The African influence appears to be substantial, with its maximum from August to October. The interplay of African vs. South American BB emissions determines the aerosol optical properties (e.g., the fractions of black vs. brown carbon, BC vs. BrC). By analyzing the diel cycles, it was found that particles from elevated aerosol-rich layers are mixed down to the canopy level in the early morning and particle number concentrations decrease towards the end of the day. Brown carbon absorption at 370 nm, σ_ap,BrC,370, was found to decrease earlier in the day, likely due to photo-oxidative processes. BC-to-CO enhancement ratios, ER_BC, reflect the variability of burnt fuels, combustion phases, and atmospheric removal processes. A wide range of ER_BC between 4 and 15 ng m⁻³ ppb⁻¹ was observed with higher values during the dry season, corresponding to the lowest ω₀ levels (0.86–0.93). The influence of the 2009/2010 and 2015/2016 El Niño periods and the associated increased fire activity on aerosol optical properties was analyzed by means of 9-year σ_sp and σ_ap time series (combination of ATTO and ZF2 data). Significant El Niño-related enhancements were observed: in the dry season, σ_sp,637 increased from 24±18 to 48±33 M m⁻¹ and σ_{ap, 637} from 3.8±2.8 to 5.3±2.5 M m⁻¹. The absorption Ångström exponent, å_abs, representing the aerosol absorption wavelength dependence, was mostly <1.0 with episodic increases upon smoke advection. A parameterization of å_abs as a function of the BC-to-OA mass ratio for Amazonian aerosol ambient measurements is presented. The brown carbon (BrC) contribution to σ_ap at 370 nm was obtained by calculating the theoretical BC å_abs, resulting in BrC contributions of 17 %–29 % (25th and 75th percentiles) to σ_ap 370 for the entire measurement period. The BrC contribution increased to 27 %–47 % during fire events under El Niño-related drought conditions from September to November 2015. The results presented here may serve as a basis to understand Amazonian atmospheric aerosols in terms of their interactions with solar radiation and the physical and chemical-aging processes that they undergo during transport. Additionally, the analyzed aerosol properties during the last two El Niño periods in 2009/2010 and 2015/2016 offer insights that could help to assess the climate change-related potential for forest-dieback feedbacks under warmer and drier conditions.

In the Amazonian atmosphere, the aerosol coarse mode comprises a complex, diverse, and variable mixture of bioaerosols emitted from the rain forest ecosystem, long-range transported Saharan dust (we use Sahara as shorthand for the dust source regions in Africa north of the Equator), marine aerosols from the Atlantic Ocean, and coarse smoke particles from deforestation fires. For the rain forest, the coarse mode particles are of significance with respect to biogeochemical and hydrological cycling, as well as ecology and biogeography. However, knowledge on the physicochemical and biological properties as well as the ecological role of the Amazonian coarse mode is still sparse. This study presents results from multi-year coarse mode measurements at the remote Amazon Tall Tower Observatory (ATTO) site. It combines online aerosol observations, selected remote sensing and modeling results, as well as dedicated coarse mode sampling and analysis. The focal points of this study are a systematic characterization of aerosol coarse mode abundance and properties in the Amazonian atmosphere as well as a detailed analysis of the frequent, pulse-wise intrusion of African long-range transport (LRT) aerosols (comprising Saharan dust and African biomass burning smoke) into the Amazon Basin. We find that, on a multi-year time scale, the Amazonian coarse mode maintains remarkably constant concentration levels (with 0.4 cm⁻³ and 4.0 µg m⁻³ in the wet vs. 1.2 cm⁻³ and 6.5 µg m⁻³ in the dry season) with rather weak seasonality (in terms of abundance and size spectrum), which is in stark contrast to the pronounced biomass burning-driven seasonality of the submicron aerosol population and related parameters. For most of the time, bioaerosol particles from the forest biome account for a major fraction of the coarse mode background population. However, from December to April there are episodic intrusions of African LRT aerosols, comprising Saharan dust, sea salt particles from the transatlantic passage, and African biomass burning smoke. Remarkably, during the core period of this LRT season (i.e., February–March), the presence of LRT influence, occurring as a sequence of pulse-like plumes, appears to be the norm rather than an exception. The LRT pulses increase the coarse mode concentrations drastically (up to 100 µg m⁻³) and alter the coarse mode composition as well as its size spectrum. Efficient transport of the LRT plumes into the Amazon Basin takes place in response to specific mesoscale circulation patterns in combination with the episodic absence of rain-related aerosol scavenging en route. Based on a modeling study, we estimated a dust deposition flux of 5–10 kg ha⁻¹ a⁻¹ in the region of the ATTO site. Furthermore, a chemical analysis quantified the substantial increase of crustal and sea salt elements under LRT conditions in comparison to the background coarse mode composition. With these results, we estimated the deposition fluxes of various elements that are considered as nutrients for the rain forest ecosystem. These estimates range from few g ha⁻¹ a⁻¹ up to several hundreds of g ha⁻¹ a⁻¹ in the ATTO region. The long-term data presented here provide a statistically solid basis for future studies of the manifold aspects of the dynamic coarse mode aerosol cycling in the Amazon. Thus, it may help to understand its biogeochemical relevance in this ecosystem as well as to evaluate to what extent anthropogenic influences have altered the coarse mode cycling already.

Deriving absorption coefficients from Aethalometer attenuation data requires different corrections to compensate for artifacts related to filter-loading effects, scattering by filter fibers, and scattering by aerosol particles. In this study, two different correction schemes were applied to seven-wavelength Aethalometer data, using multi-angle absorption photometer (MAAP) data as a reference absorption measurement at 637 nm. The compensation algorithms were compared to five-wavelength offline absorption measurements obtained with a multi-wavelength absorbance analyzer (MWAA), which serves as a multiple-wavelength reference measurement. The online measurements took place in the Amazon rainforest, from the wet-to-dry transition season to the dry season (June–September 2014). The mean absorption coefficient (at 637 nm) during this period was 1.8 ± 2.1 Mm⁻¹, with a maximum of 15.9 Mm⁻¹. Under these conditions, the filter-loading compensation was negligible. One of the correction schemes was found to artificially increase the short-wavelength absorption coefficients. It was found that accounting for the aerosol optical properties in the scattering compensation significantly affects the absorption Ångström exponent (å_ABS) retrievals. Proper Aethalometer data compensation schemes are crucial to retrieve the correct å_ABS, which is commonly implemented in brown carbon contribution calculations. Additionally, we found that the wavelength dependence of uncompensated Aethalometer attenuation data significantly correlates with the å_ABS retrieved from offline MWAA measurements.