Modelling proton and metal binding to humic substances with the NICA–EPN model

2014 ◽  
Vol 11 (3) ◽  
pp. 318 ◽  
Author(s):  
Andrea C. Montenegro ◽  
Silvia Orsetti ◽  
Fernando V. Molina
Keyword(s):  
Organic Matter ◽  
Humic Substances ◽  
Natural Organic Matter ◽  
Metal Binding ◽  
Binding Constants ◽  
Metal Cations ◽  
Electrostatic Model ◽  
Net Charge ◽  
Electrostatic Contribution ◽  
Intrinsic Mean

Environmental context The toxicity of metals in the environment is greatly influenced by natural organic matter owing to its ability to bind metals to form complexes that can be immobile and non-bioavailable. Sound mathematical models are important to reliably predict the behaviour of such contaminants, and how they are affected by organic matter and other environmental colloids. Here a new model is discussed and compared with precedent ones. Abstract The mathematical modelling of metal cation–natural organic matter interactions is a fundamental tool in predicting the state and fate of pollutants in the environment. In this work, the binding of protons and metal cations to humic substances is modelled applying the Elastic Polyelectrolyte Network (EPN) electrostatic model with the Non-Ideal Competitive Adsorption (NICA) isotherm as the intrinsic part (NICA–EPN model). Literature data of proton and metal binding to humic substances at different pH and ionic strength values are analysed, discussing in depth the model predictions. The NICA–EPN model is found to describe well these phenomena. The electrostatic contribution to the Gibbs free energy of adsorbate–humic interaction in the EPN model is lower than that predicted by the Donnan phase model; the intrinsic mean binding constants for protons and metal cations are generally higher, closer to independent estimations and to the range of acid–base and complexation equilibrium values for common carboxylic acids. The results for metal cations are consistent with recent literature findings. The model predicts shrinking of the humic particles with increased metal binding, as a consequence of net charge decrease.

scholarly journals Using water hyacinth (Eichhornia crassipes) biomass and humic substances to produce urea-based multi-coated slow release fertilizer

Cellulose ◽  
2021 ◽  
Author(s):  
Iris Amanda A. Silva ◽  
Osmir Fabiano L. de Macedo ◽  
Graziele C. Cunha ◽  
Rhayza Victoria Matos Oliveira ◽  
Luciane P. C. Romão
Keyword(s):  
Organic Matter ◽  
Humic Substances ◽  
Natural Organic Matter ◽  
Nitrogen Fertilization ◽  
Water Hyacinth ◽  
Eichhornia Crassipes ◽  
Slow Release ◽  
Leaching Tests ◽  
Slow Release Fertilizer ◽  
Atmosphere System

AbstractUrea-based multi-coated slow release fertilizer was produced using water hyacinth, humic substances, and chitosan, with water rich in natural organic matter as a solvent. Elemental analysis showed that the nitrogen content of the fertilizer (FERT) was around 20%. Swelling tests demonstrated the effectiveness of the water hyacinth crosslinker, which reduced the water permeability of the material. Leaching tests showed that FERT released a very low concentration of ammonium (0.82 mg L−1), compared to the amount released from urea (43.1 mg L−1). No nitrate leaching was observed for FERT, while urea leached 13.1 mg L−1 of nitrate. In water and soil, FERT showed maximum releases after 30 and 40 days, respectively, while urea reached maxima in just 2 and 5 days, respectively. The results demonstrated the promising ability of FERT to reduce nitrogen losses, as well as to minimize environmental impacts in the soil–plant-atmosphere system and to improve the efficiency of nitrogen fertilization. Graphic abstract

A molecular dynamic study of Soil Organic Matter stabilization mechanisms

2021 ◽  
Author(s):  
Edgar Galicia-Andrés ◽  
Yerko Escalona ◽  
Peter Grančič ◽  
Chris Oostenbrink ◽  
Daniel Tunega ◽  
...  
Keyword(s):  
Organic Matter ◽  
Soil Organic Matter ◽  
Humic Substances ◽  
Clay Mineralogy ◽  
Metal Cations ◽  
Dense Matter ◽  
Chemical Degradation ◽  
Molecular Graphics ◽  
Organic Matter Stabilization ◽  
Reactive Surfaces

<p>It is well known that some fractions of soil organic matter (SOM) can resist to physical and (bio)chemical degradation which can be attributed to factors ranging from molecular properties to the preference for digesting other molecular species by microorganisms. Some mechanisms, by which organic matter is protected, are often referred to as: physical stabilization through microaggregation, chemical stabilization by formation of SOM-mineral aggregates, and biochemical stabilization through the formation of recalcitrant SOM.</p><p>Protection mechanisms are responsible for the accumulation process of organic carbon, reducing the exposure of organic matter and making it less vulnerable to microbial, enzymatic or chemical attacks. In these mechanisms, water molecular bridges and metal cation bridges play a key role. Cation bridges serve as aggregation sites on humic substances, forming dense matter, in comparison to systems where bridges are missing. This effect is enhanced in systems with cations at higher oxidation states.</p><p>By using the modeler tool developed in our group (Vienna Soil–Organic–Matter Modeler, VSOMM2) (Escalona et al., 2021), we generated aggregate models of humic substances at atomistic scale reflecting the diversity in composition, size and conformations of the constituting molecules. Further, we built models of organo-clay aggregates using kaolinite and montmorillonite as typical soil minerals. This allowed a systematic study to understand the effect of the surrounding environment at microscopic scale, not fully accessible experimentally.</p><p>Molecular simulations of the adsorption process of SOM aggregates on the reactive surfaces of led to two observations: 1) the humic substances aggregates were able to interact with the reactive surfaces mainly via hydrogen bonds forming stable organic matter-clay complexes and 2) the aggregates subsequently lost rigidity and stability after metal cations removing, consequently leading to a gradual loss of humic substance molecules, evidencing the role of metal cations in the protection mechanism of soil organic matter aggregates and possibly explaining its recalcitrance (Galicia-Andrés et al., 2021).</p><p>References</p><ul><li>Escalona, Y., Petrov, D., & Oostenbrink, C. (2021). Vienna soil organic matter modeler 2 (VSOMM2). Journal of Molecular Graphics and Modelling, 103, 107817. https://doi.org/10.1016/j.jmgm.2020.107817</li> <li>Galicia-Andrés, E., Grančič, P., Gerzabek, M. H., Oostenbrink, C., & Tunega, D. (2021). Modeling of interactions in natural and synthetic organoclays. In I. C. Sainz Diaz (Ed.), Computational modeling in clay mineralogy.</li> </ul>

Metal ion binding by humic substances as emergent functions of labile supramolecular assemblies

2020 ◽  
Vol 17 (3) ◽  
pp. 252 ◽  
Author(s):  
Elena A. Vialykh ◽  
Dennis R. Salahub ◽  
Gopal Achari
Keyword(s):  
Molecular Weight ◽  
Organic Matter ◽  
Humic Substances ◽  
Metal Binding ◽  
Metal Ion ◽  
Computational Modelling ◽  
Intermolecular Forces ◽  
Metal Complexation ◽  
Emergent Properties ◽  
Metal Availability

Environmental contextThe fundamental basis for the high flexibility of humic substances is still unclear, though it is crucial for the understanding of metal bioavailability and toxicity in soil and aqueous environments. We show at the molecular level how characteristics of organic matter affect metal binding depending on the environmental conditions. Such understanding will help in the modulation of metal availability in soil and water in changing environmental situations. AbstractIn this work, we explore the hypothesis that humic substances (HS) can be perceived as labile supramolecular assemblages, the functioning of which is mainly determined by chemical composition and characteristics, the size of molecular units and weak intermolecular forces, rather than the exact primary structure of molecular moieties and their spatial configuration. To test the hypothesis, 72 computational models of three different organic mixtures were composed. The formation of inner and outer sphere metal–ligand complexes, metal binding sites, complex configurations, binding energies and aggregation/dissolution as emergent properties of HS were determined under various conditions. The results of computational modelling revealed that: (i) the highest Cu2+ binding (55.6%) was by the SRFA-22 organic model, which represents low-molecular-weight fulvic acids. In contrast, the highest amount of inner-sphere Mg–organic matter complex (63.4%) was formed in SRHA-6, which has higher-molecular-weight constituents. Therefore, a correlation between the type of cation, the system aromaticity and the extent of metal complexation is proposed. (ii) Increase of metal ion concentration and decrease of water content resulted in an increase in the number of hydrogen bonds and more compact and stable aggregates with lower hydrophilic and higher hydrophobic surface areas in SRFA-22. However, in SRHA-6, the results varied owing to the competition between metal binding, H-bonding and non-polar interactions in the structural arrangement of the aggregates. In general, the aggregation process, driven by metal complexation and water removal, resulted in the formation of more stable conformers, with lower potential energy, with the only exception of SRHA-6–Cu.

scholarly journals Fouling analysis of polysulfone ultrafiltration membranes used for drinking water treatment

2011 ◽  
Vol 11 (6) ◽  
pp. 668-674 ◽  
Author(s):  
B. Q. Zhao ◽  
C. P. Huang ◽  
S. Y. Chen ◽  
D. S. Wang ◽  
T. Li ◽  
...  
Keyword(s):  
Drinking Water ◽  
Organic Matter ◽  
Water Treatment ◽  
Fulvic Acid ◽  
Humic Substances ◽  
Natural Organic Matter ◽  
Drinking Water Treatment ◽  
Ultrafiltration Membranes ◽  
Fluorescence Excitation ◽  
Hydrophobic Fraction

Natural organic matter (NOM) plays a significant role in the fouling of ultrafiltration membranes in drinking water treatment processes. For a better understanding of the interaction between fractional components of NOM and polysulfone (PS) ultrafiltration membranes used for drinking water treatment, fouling and especially the physically irreversible fouling of natural organic matter were investigated. Resin fractionation, fluorescence excitation–emission matrix (EEM) spectroscopy, fourier transform infrared spectroscopy (FTIR), contact angle and a scanning electron microscope (SEM) were employed to identify the potential foulants. The results showed that humic acid and fulvic acid of small size were likely to permeate the membrane, while the hydrophobic fraction of humic and fulvic acid and aromatic proteins tended to be rejected and retained. Organic compounds such as proteins, humic substances, and polysaccharide-like materials, were all detected in the fouling layer. The physically irreversible fouling of the PS membrane seemed to be mainly attributed to the hydrophobic fraction of humic substances.

The role of humic substances in chromium sorption onto natural organic matter (peat)

Chemosphere ◽  
2006 ◽  
Vol 63 (11) ◽  
pp. 1974-1982 ◽  
Author(s):  
J. Kyziol ◽  
I. Twardowska ◽  
Ph. Schmitt-Kopplin
Keyword(s):  
Organic Matter ◽  
Humic Substances ◽  
Natural Organic Matter

scholarly journals Metal Binding and Sources of Humic Substances in Recent Sediments from the Cananéia-Iguape Estuarine-Lagoon Complex (South-Eastern Brazil)

2021 ◽  
Vol 11 (18) ◽  
pp. 8466
Author(s):  
Christian Millo ◽  
Carlo Bravo ◽  
Stefano Covelli ◽  
Elena Pavoni ◽  
Elisa Petranich ◽  
...  
Keyword(s):  
Organic Matter ◽  
Trace Metals ◽  
Humic Substances ◽  
Humic Acids ◽  
Metal Binding ◽  
Binding Capacity ◽  
Stable Carbon Isotope ◽  
Fulvic Acids ◽  
Freshwater Environment ◽  
Estuarine Lagoon

The Cananéia-Iguape estuarine–lagoon complex (São Paulo state, Brazil) is a natural laboratory to study metal binding by humic substances (HS) in subtropical settings. This transitional environment is evolving into a freshwater environment due to water input from the Ribeira River, funneled through the Valo Grande Canal (Iguape). Past mining activities in the Ribeira River basin and maritime traffic are suspected to be potential sources of trace metals in the system. In this study, the trace metal contents of Free Humic Acids (FHA), Bound Humic Acids (BHA), and Fulvic Acids (FA) extracted from sedimentary organic matter were investigated. Moreover, the sources of HS were traced using their stable carbon isotope compositions and C/N ratios. The results suggested a mixed marine–terrestrial source of FHA, BHA, and FA. Copper and Cr were the most abundant trace metals bound to HS. On average, Cu showed concentrations of 176, 115, and 37.9 μg g−1 in FHA, BHA, and FA, respectively, whereas Cr showed average concentrations of 47.4, 86.3, and 43.9 μg g−1 in FHA, BHA, and FA, respectively. Marine FHA showed the highest binding capacity for trace metals, whereas terrestrial FA derived from the decay of mangrove organic matter showed the lowest binding capacity.

scholarly journals NOM removal technologies – Norwegian experiences

2010 ◽  
Vol 3 (1) ◽  
pp. 1-9 ◽  
Author(s):  
H. Ødegaard ◽  
S. Østerhus ◽  
E. Melin ◽  
B. Eikebrokk
Keyword(s):  
Organic Matter ◽  
Activated Carbon ◽  
Humic Substances ◽  
Natural Organic Matter ◽  
Membrane Filtration ◽  
Granular Media ◽  
Physical Adsorption ◽  
Nanofiltration Membranes ◽  
Removal Technologies ◽  
Molecular Sieving

Abstract. The paper gives an overview of the methods for removal of natural organic matter (NOM) in water, particularly humic substances (HS), with focus on the Norwegian experiences. It is demonstrated that humic substances may be removed by a variety of methods, such as; molecular sieving through nanofiltration membranes, coagulation with subsequent floc separation (including granular media or membrane filtration), oxidation followed by biofiltration and sorption processes including chemisorption (ion exchange) and physical adsorption (activated carbon). All these processes are in use in Norway and the paper gives an overview of the operational experiences.

Sign in / Sign up

Export Citation Format

Share Document