Degradation of nanoplastics in aquatic environments: reactivity and impact on dissolved organic carbon

2020 ◽  
Author(s):  
Angelica Bianco ◽  
Fabrizio Sordello ◽  
Mikael Ehn ◽  
Davide Vione ◽  
Monica Passananti
Keyword(s):  
Organic Matter ◽  
Dissolved Organic Matter ◽  
Aqueous Phase ◽  
Surface Waters ◽  
High Resolution Mass Spectrometry ◽  
Degradation Products ◽  
Plastic Material ◽  
Environmental Models ◽  
Reactivity Constant ◽  
The Impact

<p>The large production of plastic material (PlasticsEurope, 2019), together with the mishandling of plastic waste, has resulted in ubiquitous plastic pollution, which now reaches even the most remote areas of the Earth (Allen et al., 2019; Bergmann et al., 2019). Plastics undergo a slow process of erosion in the environment that decreases their size: microplastics (MPs) and nanoplastics (NPs) have diameters between 1 µm and 5 mm and lower than 1 µm, respectively (Frias and Nash, 2019).</p><p>The occurrence, transformation and fate of MPs and NPs in the environment are still unclear. Therefore, the objective of this work is to better understand the reactivity of NPs using an aqueous suspension of polystyrene NPs (PS-NPs) as a proxy, in the presence of sunlight and chemicals oxidants. The results obtained are relevant to both the atmospheric aqueous phase, such as cloud and fog droplets, and surface waters. We investigated the reactivity of PS-NPs with light and with two important oxidants in the environment: ozone (O<sub>3</sub>) and hydroxyl radicals (<sup>•</sup>OH). The adsorption of ozone (O<sub>3</sub>) on PS-NPs is investigated, showing a significant O<sub>3</sub> uptake. Moreover, for the first time, a reactivity constant with <sup>•</sup>OH is determined. We found a linear correlation between the kinetic constants measured for three different sizes of PS-NPs and the surface exposed by the particles. Degradation products (short chain carboxylic acids and aromatic compounds), obtained by direct and <sup>•</sup>OH-mediated photolysis of PS-NPs suspensions, are identified by high-resolution mass spectrometry. Irradiation of a PS-NPs suspension under natural sunlight for 1 year has shown the formation of formic acid and organic compounds similar to those found in riverine and cloud dissolved organic matter.</p><p>This work is crucial to assess the impact of NPs abiotic degradation in atmospheric and surface waters; indeed, the reactivity constant and the degradation products can be implemented in environmental models to estimate the contribution of NPs degradation to the natural dissolved organic matter in the aqueous phase. A preliminary simulation using APEX (Aqueous Photochemistry of Environmentally occurring Xenobiotics) (Bodrato and Vione, 2014) model shows that in NPs-polluted environments (10<sup>9</sup> particles mL<sup>-1</sup>) there is potential for NPs to significantly scavenge <sup>•</sup>OH, if the content of natural organic matter is not too high, as observed for surface and cloud water.</p><p>Allen, S., et al., 2019.  Nat. Geosci. 12, 339–344. https://doi.org/10.1038/s41561-019-0335-5<br>Bergmann, et al., 2019.  Sci. Adv. 5, eaax1157. https://doi.org/10.1126/sciadv.aax1157<br>Bodrato, M., Vione, D., 2014. Environ. Sci.: Processes Impacts 16, 732–740. https://doi.org/10.1039/C3EM00541K<br>Frias, J., Nash, R., 2019. Mar. Pollut. Bull. 138, 145–147. https://doi.org/10.1016/j.marpolbul.2018.11.022</p>

Photochemical production of sulfate from dissolved organic matter and atmospheric aqueous phases: Is there something in common?

2020 ◽  
Author(s):  
Rachele Ossola ◽  
Baptiste Clerc ◽  
Julie Tolu ◽  
Lenny H. E. Winkel ◽  
Kristopher McNeill
Keyword(s):  
Organic Matter ◽  
Dissolved Organic Matter ◽  
Aqueous Phase ◽  
Atmospheric Chemistry ◽  
Degradation Products ◽  
Chemical Mechanism ◽  
Phase Reaction ◽  
Molecular Events ◽  
Wide Range ◽  
Terrestrial Environments

<p>In a recent study, we showed that photodegradation of dissolved organic sulfur (DOS) from a wide range of natural terrestrial environments releases sulfate (SO<sub>4</sub><sup>2–</sup>) and other small and highly oxidized S-containing compounds as degradation products, similar to what had already been reported for dissolved organic carbon, nitrogen and phosphorous. However, the underlying chemical mechanism of photoproduction of sulfate is still unknown.</p><p>To fill this knowledge gap, we selected cysteine as a DOS model compound and we investigated its photodegradation to sulfate using model sensitizers as the source of singlet oxygen (<sup>1</sup>O<sub>2</sub>) and triplet excited states (<sup>3</sup>Sens*), two photochemically produced reactive species ubiquitous in sunlit surface waters. Using a combination of steady-state photochemistry experiments, kinetic modeling and mechanistic knowledge from the biochemistry literature, we reconstructed the molecular events that likely lead to the release of sulfate. We found that the release of SO<sub>2</sub> via triplet-sensitized fragmentation of cysteine sulfinic acid, a <sup>1</sup>O<sub>2</sub> degradation product of cysteine, is a key step in the reaction mechanism. In the presence of oxygen and a photosensitizer, SO<sub>2</sub> is then rapidly oxidized to SO<sub>4</sub><sup>2–</sup>.</p><p>Interestingly, nowadays there is great interest in the atmospheric chemistry community on the same transformation (i.e., aqueous phase oxidation of SO<sub>2</sub> to SO<sub>4</sub><sup>2–</sup>) in the context of extreme haze events. Triplet-induced SO<sub>2</sub> oxidation has already been proposed as a potential aqueous phase reaction that might explain the mismatch between measured and modelled sulfate concentrations, but the mechanism of this process is still not established. Our work provides an example of how mechanistic knowledge gained on the (photo)chemical behaviour of dissolved organic matter in aquatic systems can offer insights on processes occurring in atmospheric aqueous phases.</p>

scholarly journals Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

2013 ◽  
Vol 13 (2) ◽  
pp. 1023-1037 ◽  
Author(s):  
C. Mouchel-Vallon ◽  
P. Bräuer ◽  
M. Camredon ◽  
R. Valorso ◽  
S. Madronich ◽  
...  
Keyword(s):  
Organic Matter ◽  
Dissolved Organic Matter ◽  
Water Content ◽  
Gas Phase ◽  
Aqueous Phase ◽  
Water Soluble ◽  
Chemical Mechanism ◽  
Organic Species ◽  
Cloud Water Content ◽  
Isoprene Oxidation

Abstract. The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

scholarly journals The impact of four decades of annual nitrogen addition on dissolved organic matter in a boreal forest soil

2013 ◽  
Vol 10 (3) ◽  
pp. 1365-1377 ◽  
Author(s):  
M. O. Rappe-George ◽  
A. I. Gärdenäs ◽  
D. B. Kleja
Keyword(s):  
Organic Matter ◽  
Dissolved Organic Matter ◽  
Soil Solution ◽  
Mineral Soil ◽  
Solution Concentration ◽  
Oxidative Enzymes ◽  
N Saturation ◽  
N Addition ◽  
Mineral N ◽  
The Impact

Abstract. Addition of mineral nitrogen (N) can alter the concentration and quality of dissolved organic matter (DOM) in forest soils. The aim of this study was to assess the effect of long-term mineral N addition on soil solution concentration of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) in Stråsan experimental forest (Norway spruce) in central Sweden. N was added yearly at two levels of intensity and duration: the N1 treatment represented a lower intensity but a longer duration (43 yr) of N addition than the shorter N2 treatment (24 yr). N additions were terminated in the N2 treatment in 1991. The N treatments began in 1967 when the spruce stands were 9 yr old. Soil solution in the forest floor O, and soil mineral B, horizons were sampled during the growing seasons of 1995 and 2009. Tension and non-tension lysimeters were installed in the O horizon (n = 6), and tension lysimeters were installed in the underlying B horizon (n = 4): soil solution was sampled at two-week intervals. Although tree growth and O horizon carbon (C) and N stock increased in treatments N1 and N2, the concentration of DOC in O horizon leachates was similar in both N treatments and control. This suggests an inhibitory direct effect of N addition on O horizon DOC. Elevated DON and nitrate in O horizon leachates in the ongoing N1 treatment indicated a move towards N saturation. In B horizon leachates, the N1 treatment approximately doubled leachate concentrations of DOC and DON. DON returned to control levels, but DOC remained elevated in B horizon leachates in N2 plots nineteen years after termination of N addition. We propose three possible explanations for the increased DOC in mineral soil: (i) the result of decomposition of a larger amount of root litter, either directly producing DOC or (ii) indirectly via priming of old SOM, and/or (iii) a suppression of extracellular oxidative enzymes.

scholarly journals Origin and fate of particulate and dissolved organic matter in a naturally iron-fertilized region of the Southern Ocean

2014 ◽  
Vol 11 (10) ◽  
pp. 14097-14132 ◽  
Author(s):  
L. Tremblay ◽  
J. Caparros ◽  
K. Leblanc ◽  
I. Obernosterer
Keyword(s):  
Organic Matter ◽  
Organic Carbon ◽  
Dissolved Organic Matter ◽  
Southern Ocean ◽  
Surface Waters ◽  
Bacterial Degradation ◽  
Natural Iron ◽  
Average Proportion ◽  
Carbon Pump ◽  
Microbial Carbon

Abstract. Natural iron fertilization of high-nutrient low-chlorophyll (HNLC) waters induces annually occurring spring phytoplankton blooms off Kerguelen Islands (Southern Ocean). To examine the origin and fate of particulate and dissolved organic matter (POM and DOM), D- and L-amino acids (AA) were quantified at bloom and HNLC stations. Total hydrolysable AA accounted for 21–25% of surface particulate organic carbon (%POCAA) at the bloom sites, but for 10% at the HNLC site. A marked decrease in %POCAA with depth was observed at the most productive stations leading to values between 3 and 5% below 300 m depth. AA contributed to only 0.9–4.4% of dissolved organic carbon (%DOCAA) at all stations. The only consistent vertical trend was observed at the most productive station (A3-2) where %DOCAA decreased from ∼2% in the surface waters to 0.9% near 300 m. These AA yields and other markers revealed that POM and DOM were more rapidly altered or mineralized at the bloom sites compared to the HNLC site. Different molecular markers indicated that POM mostly originated from diatoms and bacteria. The estimated average proportion of POM from intact phytoplankton cells in surface waters was 45% at the bloom station A3-2, but 14% at the HNLC site. Estimates based on D-AA yields indicated that ∼15% of POM and ∼30% of DOM was of bacterial origin (cells and cell fragments) at all stations. Surprisingly, the DOM in HNLC waters appeared less altered than the DOM from the bloom, had slightly higher dissolved AA concentrations, and showed no sign of alteration within the water column. Unfavorable conditions for bacterial degradation in HNLC regions can explain these findings. In contrast, large inputs of labile organic molecules and iron, likely stimulate the degradation of organic matter (priming effect) and the production of more recalcitrant DOM (microbial carbon pump) during iron-fertilized blooms.

scholarly journals Evidence for significant protein-like dissolved organic matter accumulation in Sea of Okhotsk sea ice

2015 ◽  
Vol 56 (69) ◽  
pp. 1-8 ◽  
Author(s):  
Mats A. Granskog ◽  
Daiki Nomura ◽  
Susann Müller ◽  
Andreas Krell ◽  
Takenobu Toyota ◽  
...  
Keyword(s):  
Organic Matter ◽  
Dissolved Organic Matter ◽  
Sea Ice ◽  
Surface Waters ◽  
Sea Of Okhotsk ◽  
Sea Water ◽  
First Year ◽  
Ice Melt ◽  
Ultraviolet Range ◽  
Considerable Excess

AbstractAbsorption and fluorescence of chromophoric dissolved organic matter (CDOM) in sea ice and surface waters in the southern Sea of Okhotsk was examined. Sea-water CDOM had featureless absorption increasing exponentially with shorter wavelengths. Sea ice showed distinct absorption peaks in the ultraviolet, especially in younger ice. Older first-year sea ice had relatively flat absorption spectra in the ultraviolet range. Parallel factor analysis (PARAFAC) identified five fluorescent CDOM components, two humic-like and three protein-like. Sea water was largely governed by humic-like fluorescence. In sea ice, protein-like fluorescence was found in considerable excess relative to sea water. The accumulation of protein-like CDOM fluorescence in sea ice is likely a result of biological activity within the ice. Nevertheless, sea ice does not contribute excess CDOM during melt, but the material released will be of different composition than that present in the underlying waters. Thus, at least transiently, the CDOM introduced during sea-ice melt might provide a more labile source of fresher protein-like DOM to surface waters in the southern Sea of Okhotsk.

Assessing disinfection byproduct risks for algal impacted surface waters and the effects of peracetic acid pre-oxidation

2020 ◽  
Vol 6 (9) ◽  
pp. 2365-2381
Author(s):  
Zachary T. Kralles ◽  
Kaoru Ikuma ◽  
Ning Dai
Keyword(s):  
Organic Matter ◽  
Dissolved Organic Matter ◽  
Surface Waters ◽  
Peracetic Acid ◽  
Disinfection Byproduct

Peracetic acid pre-oxidation of algal impacted waters can reduce formation of trihalomethanes but promote formation of haloacetonitriles, due to the degradation of dissolved organic matter and coincident release of intracellular organic matter.

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