Dissolved Organic Matter Sorption Research Articles

Interactions of manganese oxides with natural dissolved organic matter: Implications for soil organic carbon cycling

Metal (oxyhydr)oxides are key factors for the transformation and stabilization of organic carbon (OC) in soil. While sorptive interactions between Al and Fe (oxyhydr)oxides and dissolved organic matter (DOM) are well studied, the role of Mn(IV) oxides (manganates) in DOM sorption, fractionation, and oxidation has not been extensively investigated. Therefore, we examined sorptive interactions between manganates (δ-MnO2, birnessite, cryptomelane; 5 g L−1) and different DOM types (beech litter and Oa/Oe material under pine; ∼100 mg L−1 dissolved organic carbon, DOC) at pH 4 and 7 in different background electrolytes (BGE; no salt, 0.01 M NaCl or CaCl2) for up to 32 h. Changes of DOM solutions and mineral phases were assessed by solid, liquid, and gas analyses, and statistically evaluated for the effects of manganate, DOM type, pH, and BGE on DOC sorption, fractionation, and oxidative transformation. Manganates sorbed 0.2–8.7 mg OC g−1. Per unit mass, δ-MnO2 was least effective in DOC retention due to its high DOC oxidation capacity. Manganates sorbed more DOC at acidic pH and more aromatic pine than more aliphatic beech DOC, with Ca2+ generally facilitating DOC sorption. Up to 56 % of added DOC (average: 25 %) was oxidized to CO2, which is comparable to the extent of DOC respiration by soil microorganisms. DOC oxidation by δ-MnO2 and cryptomelane exceeded that of birnessite, which had the lowest specific surface area of all manganates. However, we found no difference in the efficiency of manganates to oxidize DOC, implying a similar redox activity of phyllo- and tectomanganates. More beech than pine DOM was oxidized to CO2 and an acidic pH facilitated DOC decomposition. While the presence of Na-BGE increased DOC oxidation to CO2 relative to no-salt treatments, Ca-BGE had the opposite effect, as Ca2+ apparently impeded the electron transfer from sorbed OC to structural Mn(III/IV). Contact of DOM with manganates also produced high concentrations of dissolved low-molecular-weight organic acids (mainly formate, acetate, and oxalate), accounting for up to 19 % of the initial DOC concentration. In addition, reduced specific ultraviolet absorbance of DOM solutions at 280 nm indicated preferential sorption of aromatic moieties, especially in Ca-BGE. However, in the absence of Ca2+ and at neutral pH, manganates increased the aromaticity of beech DOM, most likely due to polymerization reactions. No mineral transformations occurred after reaction of manganates with DOM, despite reductive manganate dissolution. Our results imply that soil manganates accumulate more OC in acidic soils and in presence of more aromatic DOM. However, manganates oxidatively destabilize DOC by generating CO2 and low-molecular-weight organic compounds, which is presumably more relevant in acidic soils with low concentrations of polyvalent cations and for more aliphatic DOM. The produced low-molecular-weight organic compounds may promote microbial activity and foster mineral weathering. Our results suggest a pivotal role of manganates in soil OC cycling, including the fate and bioavailability of nutrient elements associated with DOM, and in supporting ligand-promoted mineral weathering and soil formation.

Effect of biosolid-derived dissolved organic matter on orthophosphate sorption to soils depends on clay mineralogy and solution composition.

Dissolved organic matter (DOM) from biosolids can alter the sorption of orthophosphate (inorganic phosphorus (IP)) to soils and, therefore, affect the bioavailability of IP. It is not clear how clay mineralogy and solution composition interfere with DOM effects on IP sorption by soils. Hence, we studied the effect of DOM on IP sorption to five semi-arid soils dominated by either illite/smectite (I/S) or kaolinite clays. IP sorption isotherms were constructed in either NaCl or CaCl2 background solution, with and without the addition of DOM. The IP sorption capacity maxima (SMAX, Langmuir model) of the I/S soils were 33-102% higher in the presence of CaCl2, as compared to NaCl. Although DOM had no effect on the IP-SMAX in the presence of CaCl2, it increased the IP-SMAX by 35-59% in the presence of the NaCl solution. Surprisingly, DOM sorption to the I/S soils was 30-90% greater in the presence of a Na+-dominated solution, as compared to a Ca2+-dominated solution. In contrast to the I/S soils, the SMAX of the kaolinitic soil was not affected by the background electrolyte (Na+, Ca2+) or the addition of DOM. Furthermore, the addition of IP reduced the sorption of DOM to the kaolinitic soil (by up to 50%) in both background electrolyte solutions. These results highlight the contrasting roles of divalent and monovalent cations in conjunction with DOM in IP sorption to semi-arid I/S soils. We propose a new approach based on two conceptual mechanisms to explain the DOM's enhancement of IP sorption to I/S soils. (1) Under dispersion conditions in the Na+-dominated solutions, Ca2+-mediated DOM-IP complexes bind to the clay's negative planar surfaces. (2) Under flocculation conditions in the Ca+-dominated solutions, the distance between adjacent platelets decreases, reducing both the electronegative charge spillover and Ca2+ bridge-mediated DOM sorption. In contrast, the addition of DOM to kaolinite, a multi-platelet clay with a low isomorphic negative charge, reduces IP sorption due to competitive sorption on the clay's broken edges.

Stabilization of hydrophobic organic compounds in sediment using alkali-activated rice husk biochar: Enhancement of sorption by dissolved organic matter

Polycyclic aromatic hydrocarbons and phthalate esters are hydrophobic organic compounds (HOCs) that pose strong risks to aquatic and sediment ecosystems. The aim of this study was to develop a material for stabilizing (sorbing) HOCs in contaminated sediment. Activated biochar with a high surface area (called RH–NaOH) was successfully synthesized by activating rice husk biochar with an alkali (NaOH). The kinetics of HOC sorption to the RH–NaOH were described well by a three-stage intraparticle diffusion model. The sorption isotherms were adequately described by the Sips sorption model. The presence of dissolved organic matter (DOM) at environmentally relevant concentrations enhanced HOC sorption to the RH–NaOH by as much as a factor of 10, and this was mainly caused by the fulvic-acid- and humic-acid-like fractions of the DOM. The degree of sorption enhancement was predicted by the integrated volume of the fulvic-acid- and humic-acid-like fraction regions of the excitation–emission matrix that was used to characterize the DOM. The polycyclic aromatic hydrocarbon and phthalate ester stabilization efficiencies when 150 d was allowed for equilibration between the sediment and RH–NaOH to be reached were 96.5% and 94.6%, respectively. The stabilization tests indicated that HOC sorption proceeded via multiple stages with different kinetics. These stages were attributed to complex processes involving HOC and DOM sorption and desorption, HOC–DOM interactions, and HOC and HOC–DOM mixture diffusion into pores. The RH–NaOH has great potential for use as a sorbent for stabilizing HOCs in contaminated sediment.

Discriminative Behavior of Cyclodextrin Polymers against Dissolved Organic Matter: Role of Cavity Size and Sorbate Properties.

Cyclodextrin polymers (CDPs) are promising next-generation adsorbents in water purification technologies. The selectivity of the polymer derivate cross-linked with tetrafluoroterephthalonitrile (TFN-CDP) for nonionic and cationic micropollutants (MPs) over dissolved organic matter (DOM) renders the adsorbent also attractive for many analytical applications. The molecular drivers of the observed selectivity are, nonetheless, not yet fully understood. To provide new insights into the sorption mechanism, we (i) synthesized TFN-CDPs with different cavity sizes (α-, β-, γ-CDP); (ii) assessed their extraction efficiencies for selected nonionic MPs in competition with different DOM size fractions (<1, 1-3, 3-10, >10 kDa) to test for size-selectivity; and (iii) performed nontargeted, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry analysis on CDP-extracted DOM compounds (<1 kDa) to probe for molecular sorbate properties governing their selective sorption. First, no evidence of size-selectivity was obtained through either the different CD cavity sizes (i) or the two independent approaches (ii) and (iii). Second, we found a dominant impact of sorbate oxygenation and polarity on the extraction of DOM and MPs, respectively, with relatively oxygen-poor/nonpolar molecules favorably retained on all α-, β-, and γ-CDP. Third, our data indicates exclusion of an anionic matrix, such as carboxylic acids, but preferential sorption of cationic nitrogen-bearing DOM, pointing at repulsive and attractive forces with the negatively charged cross-linker as a likely reason. Therefore, we ascribe TFN-CDP's selectivity to nonpolar and electrostatic interactions between MPs/DOM and the polymer building blocks. These molecular insights can further aid in the optimization of efficient and selective sorbent design for environmental and analytical applications.

Unraveling the role of natural and pyrogenic dissolved organic matter in photodegradation of biodegradable microplastics in freshwater

Biodegradable plastic is often perceived as a possible solution for microplastic (MP) pollution. Photodegradation is an important transformation pathway of biodegradable MPs in aquatic environments. However, the influence mechanisms of dissolved organic matter (DOM) from different sources on photodegradation of biodegradable MPs are poorly understood. This study explored the role of naturally and pyrogenically sourced DOM in the photodegradation of polylactic acid (PLA) MPs. The aromatics of natural DOM (NDOM) were higher than those of biochar-sourced DOM (BDOM) and showed a stronger improvement in PLA-MPs degradation, as evidenced by particle size reduction, crystallinity increase and polymerization decrease, breakage of surface morphology, and increase in oxygen-containing functional groups on MPs’ surface (O/C increase: 65.1% for NDOM; 34.9% for BDOM). Reactive oxygen species analysis showed that the excited triplet states of DOM (3DOM*) generated by NDOM produced more •OH and 1O2 than that of BDOM, accelerating PLA-MPs photodegradation. Such photodegradation processes were further enhanced through the sorption of DOM by PLA-MPs, in which non-aromatic components were preferentially sorbed, causing the enrichment of aromatics in the solution, leading to more 3DOM* formation. This study improves the understanding of the migration and transformation of biodegradable MPs with the presence of DOM.Graphical

Unraveling the Effect of Continuously Accumulating Microplastics on the Humification of Dissolved Organic Matter in the Composting System

Microplastics (MPs) accumulation in composting systems has received considerable attention in recent years. However, the ecological risk of MPs on composting environments remains scarcely explored. This study investigated the impact of polyethylene and polyethylene terephthalate MPs on the structural evolution of dissolved organic matter (DOM) during composting. The ultraviolet, excitation–emission matrix, and Fourier transform ion cyclotron resonance mass spectroscopy collectively suggested that MPs caused DOM of compost to have lower aromaticity and fewer humic acid-like substances, particularly at the early stage of composting. This inhibition effect of MPs on the aromatization of DOM of compost was proved to result from not only the altered compost characteristics (e.g., lower pH and temperature relative to the control) but also the preferential sorption of specific DOM compositions by MPs. The sorption of DOM by MPs before and after composting showed that the protein-like components and microbial by-product analogues, which were significant substrates for humification, were found to be preferentially sorbed by two MPs and thus were prevented from being directly humified by some microorganisms. The finding would contribute to an in-depth explanation of the mechanisms by which MPs affect compost humification and provide insight into the ecological risks of MPs for composting environments.

Selective sorption and desorption of DOM in Podzol horizons — DOC and aluminium contents of leachates from a column experiment

Complexation of dissolved organic matter (DOM) with cations and minerals contributes to the stabilization of carbon in soils, and can enable the transport of metals in the environment. Hence, a proper understanding of mechanisms that control DOM binding properties in the soil is important for major environmental challenges, such as climate change and stream pollution. However, the role of DOM source in those mechanisms remains understudied. Here, we consider poorly drained tropical Podzols as a model environment to isolate effects of aluminium and DOM on sorption and desorption processes in podzolisation. We collected E- and Bh-horizons from a Brazilian coastal Podzol under tropical rainforest to conduct a column experiment, and percolated the columns with DOM collected from a stream (Stream), peat water (Peat), litter (Litter) and charred litter (Char). To quantify sorption and desorption from the columns, leachates were analysed for DOC content, aluminium content, pH, and the amount of fulvic acid relative to humic acid. The results showed large differences in DOC retention between DOM-types, which were consistent over all columns. Retention of DOC in the column varied between 25 % and 92 % for DOM-type Stream, between 33 % and 63 % for DOM-type Peat, between 22 % and 47 % for DOM-type Litter, and between 8 % and 49 % for DOM-type Char. Similarly, desorption from columns with B-horizon material highly differed between DOM-types. Percolation with DOM-types Stream and Peat caused a release of native DOC from B columns that was higher than in those percolated with water only. On the other hand, percolation of B columns with DOM-types Litter and Char caused a net DOC retention. These differences reflect that certain DOM-types hindered desorption, while other DOM-types caused active desorption. The large differences in sorption/desorption between DOM-types implies that changes in environmental conditions may highly influence the fate of soil carbon in Podzols.

Static and dynamic sorption of DOM on Bond Elute PPL and Bondesil PPL sorbents: physical-chemical characteristics

ABSTRACT The objective of this work was to study sorption of dissolved organic matter (DOM) onto Bondesil PPL and Bond Elut PPL sorbents with particular attention to impact of sorption loading on molecular composition of the DOM isolated with a use of solid phase extraction (SPE). It was shown that the batch sorption isotherms were best fitted with the Langmuir model, the sorption constants were 8.6·103 L·kgOC −1 and 10.7·103 L·kgOC −1 for Bond Elut PPL and Bondesil PPL, respectively. Breakthrough curves were satisfactorily fitted by a logistic equation; the maximum sorbent loading was 13% (wt. dissolved organic carbon) for both sorbents. The relationship between loading values and optical descriptors of the DOM at the column exit showed preferential sorption of low molecular weight aromatic DOM components in the range of low loading values (up to 4%), the similar trends were observed for size exclusion chromatography (SEC) measurements. Much lesser impact of loading onto molecular composition was observed within the range from 4 to 8% dissolved organic carbon (DOC). Given high recovery values (70–85%) in this loading range, it can be recommended as preferential for conducting DOM isolation from natural waters using SPE PPL-modified sorbents.

Selective sorption and desorption of DOM in podzol horizons — FTIR and Py-GC/MS of leachates from a column experiment

The sorption of dissolved organic matter (DOM) depends on its interaction with the soil matrix. In hydromorphic podzols, DOM reacts mainly with aluminium (Al), which is responsible for the formation of the Bh-horizon in the subsoil. In this work, we investigated whether the retention of DOM in the soil during the podzolization process is selective in relation to the molecular composition of DOM. A column experiment was conducted to study the selective retention of sorption and desorption processes under controlled conditions. Materials used in the column experiment were representative for Brazilian coastal podzols under tropical rainforest. Materials were collected from this tropical coastal podzol ecosystem, and included soil from E- and Bh-horizons, and DOM from a stream (Stream), peat water (Peat), litter (Litter) and charred litter (Char). To evaluate selective retention of DOM, both the initial DOM and its leachates were analyzed by Fourier transform infrared spectra absorption (FTIR) and pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS). The results showed preferential retention of DOM associated with biopolymers for soil columns with E-horizon material (E), E with Al nitrate (E-n), E with kaolinite (E-k) and E with gibbsite (E-h), except for Char. The composition of leachates after percolation through B horizon columns was mainly determined by desorption, and had a relatively large contribution from phenolic and carboxylic groups associated with Al and low molecular weight aromatic and N-containing pyrolysis products, while products from macromolecular materials such as cellulose were selectively retained in the columns for all DOM types. DOM from the Stream (taken during the rainy season) resembled that of desorbed OM from the B columns, reinforcing substantial desorption in the field as well. Our results suggest that sorption and desorption of OM in the hydromorphic Bh-horizon is continuous and that the selectivity of sorption is dependent on DOM source.

Temperature effects on sorption of dissolved organic matter on ferrihydrite under dynamic flow and batch conditions

AbstractAccurately predicting the effect of temperature on soil C storage remains a crucial objective in the effort to understand, mitigate, and adapt to climate change. Associations between soil organic C and short‐range order minerals like the iron hydroxide ferrihydrite contribute substantially to C sequestration, but little is known about how these associations respond to changes in temperature. We investigated the effects of temperature (7, 25, and 45 °C) and dissolved organic matter (DOM) source and fraction on DOM sorption to ferrihydrite‐coated sand in continuous flow and batch systems at circumneutral pH. Our findings demonstrate a positive relationship between temperature and adsorption, especially between 25 and 45 °C. For aquatic DOM, desorption also increased appreciably with temperature, whereas desorption of peat and soil DOM was less sensitive. More aquatic DOM adsorbed compared with soil DOM at all temperatures, but flow studies revealed that aquatic DOM also desorbed at higher rates. Modeling of DOM breakthrough curves using the advection‐diffusion equation with a modified Freundlich isotherm suggested the partition coefficient increased over time. Specific ultraviolet absorbance values of initial column effluents were low, suggesting that aromatic‐rich compounds preferentially adsorbed to the mineral surface. Our results indicate that some circumstances may favor the accumulation of DOM on iron mineral surfaces as temperature increases, potentially removing organic substrates from the accessible dissolved C pool. However, the stability of new associations likely depends on the chemical characteristics of DOM and the conditions under which it adsorbed.

Coupled Sorption and Oxidation of Soil Dissolved Organic Matter on Manganese Oxides: Nano/Sub-nanoscale Distribution and Molecular Transformation.

In soil environments, the sequestration and transformation of organic carbon are closely associated with soil minerals. Birnessite (MnO2) is known to strongly interact with soil dissolved organic matter (DOM), but the microscopic distribution and molecular transformation of soil DOM on birnessite are still poorly understood. In this study, the coupled sorption and oxidation of soil DOM on birnessite were investigated at both the microscopic scale and the molecular level. Spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) results revealed, at the nano- to sub-nanoscale, that DOM was located both on the surfaces and within the interflakes or pore spaces of birnessite, and DOM within the interflakes displayed a higher oxidation state than that on the surfaces. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) results suggested that a portion of phenolic compounds were preferentially sorbed and oxidized, resulting in the formation of compounds with higher oxygen contents and polymeric products. Our Cs-STEM and FT-ICR-MS results highlighted the significance of organo-mineral associations in the microscopic mineral structure for the reactivity of organic carbon and provided the molecular evidence for the transformation of soil DOM by birnessite, which contributed to the understanding of the dynamics of soil dissolved organic carbon.

Wildfire-Derived Pyrogenic Carbon Modulates Riverine Organic Matter and Biofilm Enzyme Activities in an In Situ Flume Experiment.

Wildfires produce large amounts of pyrogenic carbon (PyC), including charcoal, known for its chemical recalcitrance and sorption affinity for organic molecules. Wildfire-derived PyC can be transported to fluvial networks. Here it may alter the dissolved organic matter (DOM) concentration and composition as well as microbial biofilm functioning. Effects of PyC on carbon cycling in freshwater ecosystems remain poorly investigated. Employing in-stream flumes with a control versus treatment design (PyC pulse addition), we present evidence that field-aged PyC inputs to rivers can increase the dissolved organic carbon (DOC) concentration and alter the DOM composition. DOM fluorescence components were not affected by PyC. The in-stream DOM composition was altered due to leaching of pyrogenic DOM from PyC and possibly concurrent sorption of riverine DOM to PyC. Decreased DOM aromaticity indicated by a lower SUVA245 (−0.31 unit) and a higher pH (0.25 unit) was associated with changes in enzymatic activities in benthic biofilms, including a lower recalcitrance index (β-glucosidase/phenol oxidase), suggesting preferential usage of recalcitrant over readily available DOM by biofilms. The deposition of particulate PyC onto biofilms may further modulate the impacts of PyC due to direct contact with the biofilm matrix. This study highlights the importance of PyC for in-stream biogeochemical organic matter cycling in fire-affected watersheds.

Spatial and seasonal patterns of dissolved organic matter hydrophobicity in Lake Taihu revealed by the aqueous two-phase system

The hydrophobicity of dissolved organic matter (DOM) is a key property influencing the environmental risks of organic pollutants. Our understanding of the spatial and seasonal pattern of DOM hydrophobicity in aquatic systems and the major controlling factors is still limited. In this study, the hydrophobicity of 124 DOM samples collected from northern Lake Taihu, a typical eutrophic lake, was quantified using the partition coefficient of DOM in the aqueous two-phase system (KATPS). The results revealed high-resolution spatial patterns and seasonal variations of DOM hydrophobicity in Lake Taihu. The riverine input, algae activity, and photodegradation were identified as important processes shaping the spatial and seasonal pattern of DOM hydrophobicity. The riverine input and algae activity strongly affected DOM hydrophobicity in the west part and the central area of the lake. Photodegradation process played a significant role in DOM hydrophobicity in the east part of the lake in summer. The high-resolution spatial and seasonal pattern of the hydrophobic organic pollutant partition affinity of DOM (KOC) was assessed based on the two-phase system model and the KATPS dataset. The KOC values vary significantly in Lake Taihu between spring and summer, especially in the Zhushan Bay and east coast areas, highlighting the need for considering DOM dynamics in sorption assessment. Our results detailly profiled the spatial and seasonal patterns of DOM hydrophobicity and sorption behavior and elucidated the major controlling factors, which is crucial for environmental risk assessment.

Sorption of dissolved organic matter by freshwater bacterioplankton

Here we describe the study of the sorption of high-molecular components of dissolved organic matter (DOM) of natural waters - humic acids - by eight bacterial strains isolated from freshwater. Isotherms of DOM sorption by cells are described by the Langmuir equation. Gram-positive bacteria adsorb more DOM than gram-negative bacteria, with high molecular weight DOM fractions binding in a relatively selective manner. A high positive correlation (r = 0.91) was found between the decrease in the molecular weight of DOM during the sorption of these compounds by cells and the maximum sorption value. The formation of a polysaccharide capsule increases the binding of DOM by the cells of Pseudomonas sp. to the level of gram-positive bacteria.

Dissolved organic matter characteristics in soils of tropical legume and non-legume tree plantations

Dissolved organic matter (DOM) drives many fundamental biogeochemical processes (e.g., carbon storage, nutrient cycling, and soil development) in forest soil. However, the molecular-level characteristics of DOM derived from different types of tropical forest soils are poorly understood. Here, water samples at different soil depths (0, 20, and 40 cm) from tropical legume (Acacia auriculiformis, AA) and non-legume (Eucalyptus urophylla, EU) tree plantations were analyzed using absorption and fluorescence spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and solution-state 1H nuclear magnetic resonance (NMR) spectroscopy. The FT-ICR MS results indicated that DOM persisted in the soil, but its molecular composition notably shifted from low-mass (150–300 Da) and more-aromatic molecules to middle- (300–450 Da) and high-mass (>450 Da) and less-aromatic molecules with increasing soil depth. This was primarily mediated by consumption and mineral sorption of low-mass plant-derived DOM (e.g., low-mass carbohydrates and polyphenols) and further formation of larger microbial products (e.g., protein-like and lipid-like compounds). In addition, a higher abundance of microbial-derived molecules (e.g., protein-like and carboxyl-rich alicyclic molecules) was found at the legume plantation relative to the non-legume plantation, which suggests a faster microbial turnover of DOM. Also, the legume plantation had greater enrichment of middle- and high-mass and condensed aromatic-like DOM components in soils. These findings improve our understanding of the drivers that mediate the response of DOM to soil depth and tree species in tropical plantations.

The importance of aromaticity to describe the interactions of organic matter with carbonaceous materials depends on molecular weight and sorbent geometry.

Dissolved organic matter (DOM) is ubiquitous in aquatic environments where it interacts with a variety of particles including carbonaceous materials (CMs). The complexity of both DOM and the CMs makes DOM-CM interactions difficult to predict. In this study we have identified the preferential sorption of specific DOM fractions as being dependent on their aromaticity and molecular weight, as well as on the surface properties of the CMs. This was achieved by conducting sorption batch experiments with three types of DOM (humic acid, Suwannee River natural organic matter, and a compost extract) and three types of CMs (graphite, carbon nanotubes, and biochar) with different geometries and surface complexities. The non-adsorbed DOM fraction was analyzed by size exclusion chromatography and preferentially sorbed molecular weight fractions were analyzed by UV/vis and fluorescence spectroscopy. All three sorbent types were found to preferentially sorb aromatic DOM fractions, but DOM fractionation depended on the particular combination of sorbent and sorbate characteristics. Single-walled carbon nanotubes only sorbed the smaller molecular weight fractions (<1 kDa). The sorption of smaller DOM fractions was not accompanied by a preference for less aromatic compounds, contrary to what was suggested in previous studies. While graphite preferentially sorbed the most aromatic DOM fraction (1-3 kDa), the structural heterogeneity of biochar resulted in reduced selectivity, sorbing all DOM > 1 kDa. The results explain the lack of correlation found in previous studies between the amount of aromatic carbon in a bulk DOM and its sorption coefficient. DOM sorption by CMs was generally controlled by DOM aromaticity but complex sorbent surfaces with high porosity, curvatures and functional groups strongly reduced the importance of aromaticity.

Methylmercury sorption onto engineered materials.

Four commercially available sorbents (BioChar (BC), ThiolSAMMS® (TS), SediMite (SM), and Organoclay™ PM-199 (OC-199)) were tested for their ability to sorb methylmercury (MeHg) and MeHg complexed with dissolved organic matter (DOM). Testing sorption behavior with DOM is more representative of the environmental conditions and mercury speciation expected during in-situ remediation efforts. Isotherms were fit using a robust, iterative re-weighting scheme. This fitting approach improves upon the traditionally used indirect sorption method by removing the dependence between aqueous and solid phase concentrations in isotherm fitting. Developed isotherms show that without DOM, BC, TS, and SM adsorbed similar amounts of MeHg while OC-199 sorbed substantially less MeHg. Below an equilibrium concentration of 5.6 ng L-1 BC was the best performing sorbent, between 5.6 and 20.9 ng L-1 SM sorbed the most MeHg, and above an equilibrium concentration of 20.9 ng L-1 TS outperformed the other sorbents. BC and OC-199 showed indication of MeHg sorption saturation over the tested concentration range of 3.5-680 ng L-1. With DOM, SM outperformed the other sorbents at equilibrium concentrations less than 0.98 ng L-1 and TS was the superior MeHg:DOM sorbent at higher concentrations. MeHg:DOM sorption was controlled by DOM-sorbent interactions. DOM decreased MeHg sorption onto BC and SM whereas TS exhibited similar sorption with and without DOM. OC-199 had slightly higher MeHg uptake with DOM. East Fork Poplar Creek (EFPC), an industrially Hg contaminated site, was used as a case study example to build a relationship between aqueous and fish MeHg concentrations and subsequently compare the cost of sorbent materials required to meet regulatory objectives. For this case study, SM provided the most cost-effective sorbent option for in-situ remediation efforts to reduce aqueous MeHg concentrations.

Natural Photosensitizers in Constructed Unit Process Wetlands: Photochemical Characterization and Inactivation of Pathogen Indicator Organisms.

Dissolved organic matter (DOM) is a natural photosensitizer that contributes to the inactivation of microbial pathogens. In constructed treatment wetlands with open water areas DOM can promote sunlight disinfection of wastewater effluent, but a better understanding of DOM spectroscopic and photochemical properties and how they are impacted by different unit process wetlands is needed to inform design. The goals of this study were: (1) to investigate whether DOM isolates realistically represent the photochemistry of the source DOM in its original water and (2) to observe how changes of DOM along a treatment wetland affect its photochemistry, including pathogen inactivation. A pilot scale unit process wetland was studied that consisted of three different cells (open water, cattail, and bulrush) fed by secondary wastewater effluent. DOM was isolated using solid-phase extraction (SPE), photochemically characterized, and compared to the original water samples and standard DOMs. For MS2 coliphage, a virus indicator, the most efficient photosensitizer was the wastewater DOM isolated from the influent of the wetland, while for the bacterial indicator Enterococcus faecalis, inactivation results were comparable across wetland isolates. SPE resulted in isolation of 47% to 59% of whole water DOM and enriched for colored DOM. Singlet oxygen precursors were efficiently isolated, while some excited triplet state precursors remained in the extraction discharge. DOM processing indicators such as SUVA254, SUVA280, and spectral slopes including E2/ E3 ratios were reflected in the isolates. Photoinactivation of MS2 was significantly lower in both the reconstituted water samples and isolates compared to the original water sample, possibly due to disturbance of the trans-molecular integrity of DOM molecules by SPE that affects distance between MS2 and DOM sites with locally higher singlet oxygen production. For E. faecalis, results were similar in original water samples and isolates. Higher sorption of DOM to E. faecalis was roughly correlated with higher photoinactivation rates. To enhance sunlight disinfection in unit process wetlands, there is no advantage to placing open water cells after vegetated cells, as passage through the vegetated cells led to increased light absorption and lower singlet oxygen and triplet-state quantum yields and steady state concentrations.

Opposite influences of mineral-associated and dissolved organic matter on the transport of hydroxyapatite nanoparticles through soil and aggregates

The mechanism by which soil organic matter (SOM) controls nanoparticle transport through natural soils is unclear. In this study, we distinguished the specific effects of two primary SOM fractions, mineral-associated organic matter (MOM) and dissolved organic matter (DOM), on the transport of hydroxyapatite nanoparticles (nHAP) through a loamy soil under the conditions of saturated steady flow and environmentally relevant solution chemistry (1 mM NaCl at pH 7). The results showed that MOM could inhibit the transport of nHAP by decreasing electrostatic repulsion and increasing mechanical straining and hydrophobic interactions. Specifically, the presence of MOM reduced the mobility of nHAP in the bulk soil and its macroaggregates by ~4 fold and ~6 fold, respectively, and this hindered effect became further conspicuous in microaggregates (~36 fold decrease). An analysis of extended Derjaguin-Landau-Vervey-Overbeek (abbreviated as XDLVO) interactions indicated that MOM could decrease the primary energy barrier (Φmax1), primary minimum (Φmin1), and secondary minimum (Φmin2) to promote nHAP attachment. Conversely, DOM (10–50 mg L−1) favored nHAP mobility due to an increase in electrostatic repulsion among nHAP particles and between nHAP and soil surfaces. Pre-flushing soil with DOM (causing DOM sorption on soil) increased nHAP mobility by ~2 fold in the bulk soil and its macroaggregates, and this facilitated effect was furthered in microaggregates (~11 fold increase). The results of XDLVO interactions showed that DOM increased Φmax1, Φmin1, and Φmin2, producing an unfavorable effect on nHAP attachment. Mass recovery data revealed that the MOM-hindered effect was stronger than the DOM-facilitated effect on nHAP transport. This study suggested that changing SOM fractions could control the mobility of nanoparticles in the subsurface considerably.

Sorptive removal of dissolved organic matter in biologically-treated effluent by functionalized biochar and carbon nanotubes: Importance of sorbent functionality

The sorptive removal of dissolved organic matter (DOM) in biologically-treated effluent was studied by using multi-walled carbon nanotube (MWCNT), carboxylic functionalised MWCNT (MWCNT-COOH), hydroxyl functionalized MWCNT (MWCNT-OH) and functionalized biochar (fBC). DOM was dominated by hydrophilic fraction (79.6%) with a significantly lower hydrophobic fraction (20.4%). The sorption of hydrophobic DOM was not significantly affected by the sorbent functionality (∼10.4% variation) and sorption capacity followed the order of MWCNT > MWCNT-COOH > MWCNT-OH > fBC. In comparison, the sorption of hydrophilic fraction of DOM changed significantly (∼37.35% variation) with the change of sorbent functionality with adsorption capacity decreasing as MWCNT-OH > MWCNT-COOH > MWCNT > fBC. Furthermore, the affinity of adsorbents toward a hydrophilic compound (dinitrobenzene), a hydrophobic compound (pyrene) and humic acid was also evaluated to validate the proposed mechanisms. The results provided important insights on the type of sorbents which are most effective to remove different DOM fractions.