Atmospheric aerosols have complex and variable compositions and properties. While scientific interest is centered on the health and climatic effects of atmospheric aerosols, insufficient attention is ...given to their involvement in multiphase chemistry that alters their contribution as carriers of nutrients in ecosystems. However, there is experimental proof that the nutrient equilibria of both land and marine ecosystems have been disturbed during the Anthropocene period. This review study first summarizes our current understanding of aerosol chemical processing in the atmosphere as relevant to biogeochemical cycles. Then it binds together results of recent modeling studies based on laboratory and field experiments, focusing on the organic and dust components of aerosols that account for multiphase chemistry, aerosol ageing in the atmosphere, nutrient (N, P, Fe) emissions, atmospheric transport, transformation and deposition. The human-driven contribution to atmospheric deposition of these nutrients, derived by global simulations using past and future anthropogenic emissions of pollutants, is put into perspective with regard to potential changes in nutrient limitations and biodiversity. Atmospheric deposition of nutrients has been suggested to result in human-induced ecosystem limitations with regard to specific nutrients. Such modifications favor the development of certain species against others and affect the overall functioning of ecosystems. Organic forms of nutrients are found to contribute to the atmospheric deposition of the nutrients N, P and Fe by 20%-40%, 35%-45% and 7%-18%, respectively. These have the potential to be key components of the biogeochemical cycles since there is initial proof of their bioavailability to ecosystems. Bioaerosols have been found to make a significant contribution to atmospheric sources of N and P, indicating potentially significant interactions between terrestrial and marine ecosystems. These results deserve further experimental and modeling studies to reduce uncertainties and understand the feedbacks induced by atmospheric deposition of nutrients to ecosystems.
Atmospheric inputs of nutrients to the Mediterranean Sea Kanakidou, Maria; Myriokefalitakis, Stelios; Tsagkaraki, Maria
Deep-sea research. Part II, Topical studies in oceanography,
January 2020, 2020-01-00, Letnik:
171
Journal Article
Recenzirano
The Mediterranean Sea is an oligotrophic semi-closed environment where atmospheric deposition is expected to be an important driver for biological activity. The present study uses a three-dimensional ...atmospheric chemistry transport model to evaluate the nitrogen (N), phosphorus (P) and iron (Fe) atmospheric deposition fluxes to the Mediterranean Sea. The model takes into account both the inorganic and organic fractions of these fluxes and compares them to other sources of these nutrients that are external to the ocean. The estimated atmospheric deposition fluxes of soluble nutrients amount to 1281 Gg-N y−1, 4.31 Gg-P y−1 and 6.32 Gg-Fe y−1 for the present day, and are within the range of the few estimates available in literature. An almost 6-fold increase in the atmospheric deposition of soluble N is also calculated to be the result of the increase in anthropogenic and biomass burning emissions since 1850, while soluble P and Fe deposition fluxes have increased by 59% and 114%, respectively. For future (2100) emissions, however, N deposition is projected to increase only slightly (4%) while soluble P and Fe fluxes will decrease by 34% and 32% compared to current estimates.
The soluble organic N and P annual deposition fluxes are calculated to be 12% and 28–83% of total soluble N and P present-day annual deposition fluxes into the Mediterranean Sea, respectively. However, to reconcile with the observed fluxes in the west and the east Mediterranean, ∼14 times higher flux of soluble P, in particular organic P, and at least 2.5 times higher flux of soluble Fe need to be considered in the model. Such high fluxes can be due to higher combustion emissions of soluble Fe and P, to higher dust emissions or solubilisation of Fe and P contained in dust aerosols, and also higher organic P flux associated with bioaerosols than currently used in the global models. Overall, the calculated deposition fluxes provide an integrated spatially complete picture of the atmospheric inputs to the Mediterranean marine ecosystem, which are potentially important for net primary production and the ocean carbon cycle.
Particle water (liquid water content, LWC) and aerosol pH are important parameters of the aerosol phase, affecting heterogeneous chemistry and bioavailability of nutrients that profoundly impact ...cloud formation, atmospheric composition, and atmospheric fluxes of nutrients to ecosystems. Few measurements of in situ LWC and pH, however, exist in the published literature. Using concurrent measurements of aerosol chemical composition, cloud condensation nuclei activity, and tandem light scattering coefficients, the particle water mass concentrations associated with the aerosol inorganic (Winorg) and organic (Worg) components are determined for measurements conducted at the Finokalia atmospheric observation station in the eastern Mediterranean between June and November 2012. These data are interpreted using the ISORROPIA-II thermodynamic model to predict the pH of aerosols originating from the various sources that influence air quality in the region. On average, closure between predicted aerosol water and that determined by comparison of ambient with dry light scattering coefficients was achieved to within 8 % (slope = 0.92, R2 = 0.8, n = 5201 points). Based on the scattering measurements, a parameterization is also derived, capable of reproducing the hygroscopic growth factor (f(RH)) within 15 % of the measured values. The highest aerosol water concentrations are observed during nighttime, when relative humidity is highest and the collapse of the boundary layer increases the aerosol concentration. A significant diurnal variability is found for Worg with morning and afternoon average mass concentrations being 10–15 times lower than nighttime concentrations, thus rendering Winorg the main form of particle water during daytime. The average value of total aerosol water was 2.19 ± 1.75 µg m−3, contributing on average up to 33 % of the total submicron mass concentration. Average aerosol water associated with organics, Worg, was equal to 0.56 ± 0.37 µg m−3; thus, organics contributed about 27.5 % to the total aerosol water, mostly during early morning, late evening, and nighttime hours.The aerosol was found to be highly acidic with calculated aerosol pH varying from 0.5 to 2.8 throughout the study period. Biomass burning aerosol presented the highest values of pH in the submicron fraction and the lowest values in total water mass concentration. The low pH values observed in the submicron mode and independently of air mass origin could increase nutrient availability and especially P solubility, which is the nutrient limiting sea water productivity of the eastern Mediterranean.
Oxidative potential (OP), which is the ability of certain components in atmospheric particles to generate reactive oxidative species (ROS) and deplete antioxidants in vivo, is a prevailing ...toxicological mechanism underlying the adverse health effects associated with exposure to ambient aerosols. While previous studies have identified the high OP of fresh biomass burning organic aerosols (BBOA), it remains unclear how it evolves throughout atmospheric transport. Using the dithiothreitol (DTT) assay as a measure of OP, a combination of field observations and laboratory experiments is used to determine how atmospheric aging transforms the intrinsic OP (OPmass DTT) of BBOA. For ambient BBOA collected during the fire seasons in Greece, OPmass DTT was observed to increase by a factor of 2.1 ± 0.9 for samples of atmospheric ages up to 68 h. Laboratory experiments indicate that aqueous photochemical aging (aging by UVB and UVA photolysis; as well as OH oxidation), as well as aging by ozone and atmospheric dilution can transform the OPmass DTT of the water-soluble fraction of wood smoke within 2 days of atmospheric transport. The results from this work suggest that the air quality impacts of biomass burning emissions can extend beyond regions near fire sites and should be accounted for.
In order to investigate the secondary organic aerosol (SOA) response to changes in biogenic volatile organic compounds (VOC) emissions in the future atmosphere and how important will SOA be relative ...to the major anthropogenic aerosol component (sulfate), the global three-dimensional chemistry/transport model TM3 has been used. Emission estimates of biogenic VOC (BVOC) and anthropogenic gases and particles from the literature for the year 2100 have been adopted.
According to our present-day model simulations, isoprene oxidation produces 4.6
Tg
SOA
yr
−1, that is less than half of the 12.2
Tg
SOA
yr
−1 formed by the oxidation of other BVOC. In the future, nitrate radicals and ozone become more important than nowadays, but remain minor oxidants for both isoprene and aromatics. SOA produced by isoprene is estimated to almost triple, whereas the production from other BVOC more than triples. The calculated future SOA burden change, from 0.8
Tg at present to 2.0
Tg in the future, is driven by changes in emissions, oxidant levels and pre-existing particles. The non-linearity in SOA formation and the involved chemical and physical feedbacks prohibit the quantitative attribution of the computed changes to the above-mentioned individual factors. In 2100, SOA burden is calculated to exceed that of sulfate, indicating that SOA might become more important than nowadays. These results critically depend on the biogenic emissions and thus are subject to the high uncertainty associated with these emissions estimated due to the insufficient knowledge on plant response to carbon dioxide changes. Nevertheless, they clearly indicate that the change in oxidants and primary aerosol caused by human activities can contribute as much as the change in BVOC emissions to the increase of the biogenic SOA production in the future atmosphere.
Ecosystem productivity is strongly modulated by the atmospheric deposition of inorganic reactive nitrogen (the sum of ammonium and nitrate). The individual contributions of ammonium and nitrate vary ...considerably over space and time, giving rise to complex patterns of nitrogen deposition. In the absence of rain, much of this complexity is driven by the large difference between the dry deposition velocity of nitrogen-containing molecules in the gas or condensed phase. Here we quantify how aerosol liquid water and acidity, through their impact on gas–particle partitioning, modulate the deposition velocity of total NH3 and total HNO3 individually while simultaneously affecting the dry deposition of inorganic reactive nitrogen. Four regimes of deposition velocity emerge: (i) HNO3 – fast, NH3 – slow, (ii) HNO3 – slow, NH3 – fast, (iii) HNO3 – fast, NH3 – fast, and (iv) HNO3 – slow, NH3 – slow. Conditions that favor partitioning of species to the aerosol phase strongly reduce the local deposition of reactive nitrogen species and promote their accumulation in the boundary layer and potential for long-range transport. Application of this framework to select locations around the world reveals fundamentally important insights: the dry deposition of total ammonia displays little sensitivity to pH and liquid water variations, except under conditions of extreme acidity and/or low aerosol liquid water content. The dry deposition of total nitric acid, on the other hand, is quite variable, with maximum deposition velocities (close to gas deposition rates) found in the eastern United States and minimum velocities in northern Europe and China. In the latter case, the low deposition velocity leads to up to 10-fold increases in PM2.5 nitrate aerosol, thus contributing to the high PM2.5 levels observed during haze episodes. In this light, aerosol pH and associated liquid water content can be considered to be control parameters that drive dry deposition flux and can accelerate the accumulation of aerosol contributing to intense haze events throughout the globe.
The atmospheric cycle of phosphorus (P) is parameterized here in a state-of-the-art global 3-D chemistry transport model, taking into account primary emissions of total P (TP) and soluble P (DP) ...associated with mineral dust, combustion particles from natural and anthropogenic sources, bioaerosols, sea spray and volcanic aerosols. For the present day, global TP emissions are calculated to be roughly 1.33 Tg-P yr−1, with the mineral sources contributing more than 80 % to these emissions. The P solubilization from mineral dust under acidic atmospheric conditions is also parameterized in the model and is calculated to contribute about one-third (0.14 Tg-P yr−1) of the global DP atmospheric source. To our knowledge, a unique aspect of our global study is the explicit modeling of the evolution of phosphorus speciation in the atmosphere. The simulated present-day global annual DP deposition flux is 0.45 Tg-P yr−1 (about 40 % over oceans), showing a strong spatial and temporal variability. Present-day simulations of atmospheric P aerosol concentrations and deposition fluxes are satisfactory compared with available observations, indicating however an underestimate of about 70 % on current knowledge of the sources that drive the P atmospheric cycle. Sensitivity simulations using preindustrial (year 1850) anthropogenic and biomass burning emission scenarios showed a present-day increase of 75 % in the P solubilization flux from mineral dust, i.e., the rate at which P is converted into soluble forms, compared to preindustrial times, due to increasing atmospheric acidity over the last 150 years. Future reductions in air pollutants due to the implementation of air-quality regulations are expected to decrease the P solubilization flux from mineral dust by about 30 % in the year 2100 compared to the present day. Considering, however, that all the P contained in bioaerosols is readily available for uptake by marine organisms, and also accounting for all other DP sources, a total bioavailable P flux of about 0.17 Tg-P yr−1 to the oceans is derived. Our calculations further show that in some regions more than half of the bioavailable P deposition flux to the ocean can originate from biological particles, while this contribution is found to maximize in summer when atmospheric deposition impact on the marine ecosystem is the highest due to ocean stratification. Thus, according to this global study, a largely unknown but potentially important role of terrestrial bioaerosols as suppliers of bioavailable P to the global ocean is also revealed. Overall, this work provides new insights to the atmospheric P cycle by demonstrating that biological materials are important carriers of bioavailable P, with very important implications for past and future responses of marine ecosystems to global change.
Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric ...processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H⁺ ions present. For H⁺ < 10−4 mol/g of dust, 1–10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H⁺ > 10−4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H⁺ consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79–96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean).
This work reports on the current status of the global modeling of iron (Fe)
deposition fluxes and atmospheric concentrations and the analyses of the
differences between models, as well as between ...models and observations. A
total of four global 3-D chemistry transport (CTMs) and general circulation
(GCMs) models participated in this intercomparison, in the framework of
the United Nations Joint Group of Experts on the Scientific Aspects of Marine
Environmental Protection (GESAMP) Working Group 38, “The Atmospheric Input
of Chemicals to the Ocean”. The global total Fe (TFe) emission strength in
the models is equal to ∼72 Tg Fe yr−1 (38–134 Tg Fe yr−1)
from mineral dust sources and around 2.1 Tg Fe yr−1 (1.8–2.7 Tg Fe yr−1)
from combustion processes (the sum of anthropogenic
combustion/biomass burning and wildfires). The mean global labile Fe (LFe)
source strength in the models, considering both the primary emissions and the
atmospheric processing, is calculated to be 0.7 (±0.3) Tg Fe yr−1,
accounting for both mineral dust and combustion aerosols. The
mean global deposition fluxes into the global ocean are estimated to be in the range
of 10–30 and 0.2–0.4 Tg Fe yr−1 for TFe and LFe, respectively,
which roughly corresponds to a respective 15 and 0.3 Tg Fe yr−1 for the multi-model ensemble model mean. The model intercomparison analysis indicates that the representation of the
atmospheric Fe cycle varies among models, in terms of both the magnitude of
natural and combustion Fe emissions as well as the complexity of atmospheric
processing parameterizations of Fe-containing aerosols. The model comparison
with aerosol Fe observations over oceanic regions indicates that most models
overestimate surface level TFe mass concentrations near dust source
regions and tend to underestimate the low concentrations observed in remote
ocean regions. All models are able to simulate the tendency of higher Fe
concentrations near and downwind from the dust source regions, with the mean
normalized bias for the Northern Hemisphere (∼14), larger
than that of the Southern Hemisphere (∼2.4) for the ensemble model
mean. This model intercomparison and model–observation comparison study
reveals two critical issues in LFe simulations that require further
exploration: (1) the Fe-containing aerosol size distribution and (2) the
relative contribution of dust and combustion sources of Fe to labile Fe in
atmospheric aerosols over the remote oceanic regions.
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