Natural organic matter (NOM) serve as precursors for disinfection byproducts (DBPs) in drinking water production making NOM removal essential in predisinfection treatment processes. We identified ...molecular formulas of chlorinated DBPs after chlorination and chloramination in four Swedish surface water treatment plants (WTPs) using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chlorine-containing formulas were detected before and after disinfection and were therefore classified to identify DBPs. In total, 499 DBPs were detected, of which 230 have not been reported earlier. The byproducts had, as a group, significantly lower ratio of hydrogen to carbon (H/C) and significantly higher average carbon oxidation state (COS ), double bond equivalents per carbon (DBE/C) and ratio of oxygen to carbon (O/C) compared to Cl-containing components present before disinfection and CHO formulas in samples taken both before and after disinfection. Electrophilic substitution, the proposed most significant reaction pathway for chlorination of NOM, results in carbon oxidation and decreased H/C while O/C and DBE/C is left unchanged. Because the identified DBPs had significantly higher DBE/C and O/C than the CHO formulas we concluded that chlorination of NOM during disinfection is selective toward components with relatively high double bond equivalency and number of oxygen atoms per carbon. Furthermore, choice of disinfectant, dose, and predisinfection treatment at the different WTPs resulted in distinct patterns in the occurrence of DBP formulas.
Inland waters transport large amounts of dissolved organic matter (DOM) from terrestrial environments to the oceans, but DOM also reacts en route, with substantial water column losses by ...mineralization and sedimentation. For DOM transformations along the aquatic continuum, lakes play an important role as they retain waters in the landscape allowing for more time to alter DOM. We know DOM losses are significant at the global scale, yet little is known about how the reactivity of DOM varies across landscapes and climates. DOM reactivity is inherently linked to its chemical composition. We used fluorescence spectroscopy to explore DOM quality from 560 lakes distributed across Sweden and encompassed a wide climatic gradient typical of the boreal ecozone. Six fluorescence components were identified using parallel factor analysis (PARAFAC). The intensity and relative abundance of these components were analyzed in relation to lake chemistry, catchment, and climate characteristics. Land cover, particularly the percentage of water in the catchment, was a primary factor explaining variability in PARAFAC components. Likewise, lake water retention time influenced DOM quality. These results suggest that processes occurring in upstream water bodies, in addition to the lake itself, have a dominant influence on DOM quality. PARAFAC components with longer emission wavelengths, or red‐shifted components, were most reactive. In contrast, protein‐like components were most persistent within lakes. Generalized characteristics of PARAFAC components based on emission wavelength could ease future interpretation of fluorescence spectra. An important secondary influence on DOM quality was mean annual temperature, which ranged between −6.2 and +7.5 °C. These results suggest that DOM reactivity depends more heavily on the duration of time taken to pass through the landscape, rather than temperature. Projected increases in runoff in the boreal region may force lake DOM toward a higher overall amount and proportion of humic‐like substances.
Riverine transport of iron (Fe) and arsenic (As) is affected by their associations with natural organic matter (NOM) and suspended iron (oxy)hydroxides. Speciation has a strong influence on element ...transport from the headwaters to the ocean because NOM may be transported over longer distances compared to iron (oxy)hydroxides. We show that Fe speciation changes along the flow path of a boreal watercourse, as water moves from NOM-rich, acidic first-order streams with pH as low as 3.9 to less acidic higher-order systems (up to pH 6.4). Analysis by Flow Field-Flow Fractionation and chemical equilibrium modeling revealed that Fe from wetland-dominated headwaters was mainly exported as Fe-NOM complexes; in catchments with a stream order >1 and with higher pH, Fe was present in Fe-NOM complexes and precipitated as nanoparticulate iron(oxy)hydroxides which aggregated as the pH increased, with their size eventually exceeding the membrane filters cutoff (0.2 μm). The measured NOM-bound Fe decreased with increasing pH, from 0.38 to 0.16 mmol Fe·gNOM –1. The high concentrations of NOM-bound Fe emphasize the importance of boreal catchments to Fe export to the oceans. Concentrations of As in the <0.2 μm fraction but larger than what is usually considered “truly dissolved” (<1000 g·mol–1), decreased from 75% to 26% with increasing pH. The As in this size range was mainly associated with NOM but at pH >4.5 became associated with iron(oxy)hydroxides, and its transport thus became more coupled to that of the iron(oxy)hydroxides downstream in the circumneutral streams.
Plant nutrients can be recycled through microbial
decomposition of organic matter but replacement of base cations and
phosphorus, lost through harvesting of biomass/biofuels or leaching,
requires de ...novo supply of fresh nutrients released through weathering of soil
parent material (minerals and rocks). Weathering involves physical and
chemical processes that are modified by biological activity of plants,
microorganisms and animals. This article reviews recent progress made in
understanding biological processes contributing to weathering. A perspective
of increasing spatial scale is adopted, examining the consequences of
biological activity for weathering from nanoscale interactions, through in vitro and
in planta microcosm and mesocosm studies, to field experiments, and finally ecosystem
and global level effects. The topics discussed include the physical
alteration of minerals and mineral surfaces; the composition, amounts,
chemical properties, and effects of plant and microbial secretions; and the
role of carbon flow (including stabilisation and sequestration of C in organic
and inorganic forms). Although the predominant focus is on the effects of
fungi in forest ecosystems, the properties of biofilms, including bacterial
interactions, are also discussed. The implications of these biological
processes for modelling are discussed, and we attempt to identify some key
questions and knowledge gaps, as well as experimental approaches and areas
of research in which future studies are likely to yield useful results. A
particular focus of this article is to improve the representation of the
ways in which biological processes complement physical and chemical
processes that mobilise mineral elements, making them available for plant
uptake. This is necessary to produce better estimates of weathering that are
required for sustainable management of forests in a post-fossil-fuel
economy. While there are abundant examples of nanometre- and micrometre-scale
physical interactions between microorganisms and different minerals, opinion
appears to be divided with respect to the quantitative significance of these
observations for overall weathering. Numerous in vitro experiments and microcosm
studies involving plants and their associated microorganisms suggest that
the allocation of plant-derived carbon, mineral dissolution and plant
nutrient status are tightly coupled, but there is still disagreement about
the extent to which these processes contribute to field-scale observations.
Apart from providing dynamically responsive pathways for the allocation of
plant-derived carbon to power dissolution of minerals, mycorrhizal mycelia
provide conduits for the long-distance transportation of weathering products
back to plants that are also quantitatively significant sinks for released
nutrients. These mycelial pathways bridge heterogeneous substrates, reducing
the influence of local variation in C:N ratios. The production of
polysaccharide matrices by biofilms of interacting bacteria and/or fungi at
interfaces with mineral surfaces and roots influences patterns of
production of antibiotics and quorum sensing molecules, with concomitant
effects on microbial community structure, and the qualitative and
quantitative composition of mineral-solubilising compounds and weathering
products. Patterns of carbon allocation and nutrient mobilisation from both
organic and inorganic substrates have been studied at larger spatial and
temporal scales, including both ecosystem and global levels, and there is a
generally wider degree of acceptance of the “systemic” effects of
microorganisms on patterns of nutrient mobilisation. Theories about the
evolutionary development of weathering processes have been advanced but
there is still a lack of information connecting processes at different
spatial scales. Detailed studies of the liquid chemistry of local weathering
sites at the micrometre scale, together with upscaling to soil-scale
dissolution rates, are advocated, as well as new approaches involving stable
isotopes.
Drinking water treatment plants (DWTPs) are constantly adapting to a host of emerging threats including the removal of micro-pollutants like perfluoroalkyl substances (PFASs), while concurrently ...considering how background levels of dissolved organic matter (DOM) influences their removal efficiency. Two adsorbents, namely anion exchange (AE) and granulated active carbon (GAC) have shown particular promise for PFAS removal, yet the influence of background levels of DOM remains poorly explored. Here we considered how the removal efficiency of 13 PFASs are influenced by two contrasting types of DOM at four concentrations, using both AE (Purolite A-600®) and GAC (Filtrasorb 400®). We placed emphasis on the pre-equilibrium conditions to gain better mechanistic insight into the dynamics between DOM, PFASs and adsorbents. We found AE to be very effective at removing both PFASs and DOM, while largely remaining resistant to even high levels of background DOM (8 mg carbon L−1) and surprisingly found that smaller PFASs were removed slightly more efficiently than longer chained counterparts, In contrast, PFAS removal efficiency with GAC was highly variable with PFAS chain length, often improving in the presence of DOM, but with variable response based on the type of DOM and PFAS chain length.
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•Anion exchange was highly effective for the removal of perfluoroalkyl substances.•Short chained perfluoroalkyl substances removed effectively with anion exchange.•Perfluoroalkyl removal efficiency robust to organic matter with anion exchange.•Perfluoroalkyl removal highly variable with granulated active carbon adsorbant.
The Mars Science Laboratory spacecraft, containing the Curiosity rover, was launched to Mars on 26 November 2011, and for most of the 253-day, 560-million-kilometer cruise to Mars, the Radiation ...Assessment Detector made detailed measurements of the energetic particle radiation environment inside the spacecraft. These data provide insights into the radiation hazards that would be associated with a human mission to Mars. We report measurements of the radiation dose, dose equivalent, and linear energy transfer spectra. The dose equivalent for even the shortest round-trip with current propulsion systems and comparable shielding is found to be 0.66 ± 0.12 sievert.
Increased color in surface waters, or browning, can alter lake ecological function, lake thermal stratification and pose difficulties for drinking water treatment. Mechanisms suggested to cause ...browning include increased dissolved organic carbon (DOC) and iron concentrations, as well as a shift to more colored DOC. While browning of surface waters is widespread and well documented, little is known about why some lakes resist it. Here, we present a comprehensive study of Mälaren, the third largest lake in Sweden. In Mälaren, the vast majority of water and DOC enters a western lake basin, and after approximately 2.8 years, drains from an eastern basin. Despite 40 years of increased terrestrial inputs of colored substances to western lake basins, the eastern basin has resisted browning over this time period. Here we find the half-life of iron was far shorter (0.6 years) than colored organic matter (A₄₂₀; 1.7 years) and DOC as a whole (6.1 years). We found changes in filtered iron concentrations relate strongly to the observed loss of color in the western basins. In addition, we observed a substantial shift from colored DOC of terrestrial origin, to less colored autochthonous sources, with a substantial decrease in aromaticity (-17%) across the lake. We suggest that rapid losses of iron and colored DOC caused the limited browning observed in eastern lake basins. Across a wider dataset of 69 Swedish lakes, we observed greatest browning in acidic lakes with shorter retention times (< 1.5 years). These findings suggest that water residence time, along with iron, pH and colored DOC may be of central importance when modeling and projecting changes in brownification on broader spatial scales.
Controlled aggregation of polymer nanoparticles for building anisotropic nano- and microstructures via a self-assembling bottom-up process is an important strategy. Therefore, in this work, the ...formation of structured poly(methyl methacrylate) (PMMA) particles with diameters between lower micrometer and submicrometer range by use of a microcontinuous flow arrangement was investigated in the presence of nonionic water-soluble polymer polyvinylpyrrolidone (PVP). The investigations show that the microreaction strategy is well applicable and allows a tuning of size and shape of nanoparticles in dependence on reactant concentrations and flow rate ratios. Larger and complex structured polymer particles have been found at lower PVP concentration, whereas more compact submicron-sized particles were formed at higher PVP concentrations. The addition of ionic surfactants modulates the generation of characteristic particle shapes. The observation of intermediate states between complex flowerlike particles and simple spheres in dependence on the applied concentration of low molecular weight surfactants supports the explanation of particle formation by a mechanism with superposition of particle growth and assembling. When mixed surfactants (PVP–SDS or PVP–CTAB) are used, the final particles shape depends on the concentration of individual concentrations of surfactants and on the competition between mobility, solvation, and micelle formations.
In this paper, a microfluidic approach has been used for the synthesis of ellipsoidal, dumbbell, rodlike, and necklacelike polymer nanoparticles. High yields of special types of nonspherical ...nanoparticles have been achieved by the implementation of an emulsion polymerization into microfluidic arrangement with a micro hole-plate reactor for the formation of monomer droplets. Here, in particular, the formation of nonspherical polymer nanoparticles is dependent on the presence of polyelectrolyte surface active molecules such as poly(4-styrenesulfonic acid-co-maleic acid) sodium salt (PSS-co-PM), poly(sodium-p-styrenesulfonate) (PSSS), and polyanetholesulfonic acid sodium salt (PAES). The shapes and sizes of the interparticle nanoassemblies are precisely controlled by adjusting the concentration of polyelectrolytes in the aqueous phase, and by choosing suitable flow rate ratios (aqueous to monomer phase), respectively. The formation of polymer nanoparticles with different morphologies can be explained by a spontaneous in situ assembling under partial electrostatic repulsive control in the single step synthesis. The effect of particle charge and the competition between thermal motion of particles and electrostatic repulsion on the spontaneous assembling under the condition of a limited polarizability are discussed here as an important factor for the formation process of nonspherical polymer nanoparticles.
Particulate polymers at the nanoscale are exceedingly promising for diversified functional applications ranging from biomedical and energy to sensing, labeling, and catalysis. Tailored structural ...features (i.e., size, shape, morphology, internal softness, interior cross-linking, etc.) determine polymer nanoparticles’ impact on the cargo loading capacity and controlled/sustained release, possibility of endocytosis, degradability, and photostability. The designed interfacial features, however (i.e., stimuli-responsive surfaces, wrinkling, surface porosity, shell-layer swellability, layer-by-layer surface functionalization, surface charge, etc.), regulate nanoparticles’ interfacial interactions, controlled assembly, movement and collision, and compatibility with the surroundings (e.g., solvent and biological environments). These features define nanoparticles’ overall properties/functions on the basis of homogeneity, stability, interfacial tension, and minimization of the surface energy barrier. Lowering of the resultant outcomes is directly influenced by inhomogeneity in the structural and interfacial design through the structure–function relationship. Therefore, a key requirement is to produce well-defined polymer nanoparticles with controlled characteristics. Polymers are amorphous, flexible, and soft, and hence controlling their structural/interfacial features through the single-step process is a challenge. The microfluidics reaction strategy is very promising because of its wide range of advantages such as efficient reactant mixing and fast phase transfer. Overall, this feature article highlights the state-of-the-art synthetic features of polymer nanoparticles with perspectives on their advanced applications.
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