Dissolved Organic Matter Binding Research Articles

Effects of Cu(II)-DOM complexation on DOM degradation: Insights from spectroscopic evidence

The fate of dissolved organic matter (DOM) is primarily governed by its sources, degradation, and transformation processes within the environment. However, the influence of metal-DOM complexation on DOM degradation remains ambiguous. In this study, controlled laboratory experiments were conducted using Cu(II) and natural water from the Duliujian River and the Beidagang Wetland to examine the effects of metal-DOM binding on the degradation pathway of DOM. Our results showed that Cu(II)-DOM complexation affected the distribution of DOM molecular weight with elevated Mw after complexed with Cu(II). Nevertheless, the concentration of DOM decreased over the incubation period due to degradation. In the absence of Cu(II) binding, both wetland and river DOM followed similar degradation pathways, transforming from high to low molecular weight with changes predominantly in the 1–10 kDa size-fraction during DOM degradation. In contrast, in the presence of Cu(II) and thus Cu(II)-DOM binding, the degradation of DOM was enhanced, resulting in higher kinetic rate constants for both wetland and river DOM. The results of differential spectra further confirmed the degradation of DOM with a decrease in bulk spectroscopic properties and an increase in the degree of DOM-Cu(II) complexation. These findings imply a mutually reinforcing relationship between metal-DOM complexation and the degradation of DOM in aquatic environments, providing new insights into the biogeochemical behavior and environmental fate of DOM.

The effect and spectral response mechanism of dissolved organic matter (DOM) in Pb(II) adsorption onto biochar

This study investigated the interaction of biochar-derived dissolved organic matter (DOM) and metal pollutant Pb(II) during adsorption. Research data showed that the adsorption capacity of biochar and residual biochar (after removal of DOM) was 277.62 and 204.47 mg g−1, respectively, indicating that DOM played a significant role in enhancing the adsorption efficiency of Pb(II). The results indicated that the adsorption process of Pb(II) on biochar and residual biochar followed the pseudo-second-order kinetic equation (R2 > 0.99), and the adsorption isotherm was much closer Freundlich model. A combination of three-dimensional excitation-emission matrix (3D-EEM), synchronous fluorescence, Fourier transform infrared spectroscopy (FT-IR), and two-dimensional correlation spectroscopy (2D-COS) was employed to investigate the interaction between DOM and Pb(II). 3D-EEM indicated the presence of four major components of DOM, namely two protein-like substances, one humic acid-like substance, and one fulvic acid-like substance. The synchronous fluorescence revealed a gradual quenching of the fluorescence of the DOM sample with an increase in Pb(II) concentration, indicating a static quenching mechanism between DOM and Pb(II). FTIR-2D-COS analysis showed a specific sequence of DOM binding with Pb(II) is as follows: 1500 > 1010 > 880 > 1390 > 1260 cm−1. This findings have significant implications for the role of DOM in environmental science and have potential applications in various fields.

Dissolved organic matter mediated dark- and photo-aging processes of Hg(II): Critical impacts of binding sites and sulfidation on Hg(II) abiotic reduction and microbial methylation

Dissolved organic matter (DOM)-mediated divalent mercury (Hg(II)) aging kinetics play a crucial role in controlling Hg(II) transformation and bioavailability in natural aquatic environments. However, the differential environmental behaviors of new and aged Hg(II) in a same reaction system remains unknown. In this study, multi-isotope tracing was used to investigate the impacts of binding site and sulfidation during DOM-mediated Hg(II) aging processes on Hg(II) reduction and microbial methylation in the same reaction system. Stepwise reduction approach and liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) demonstrate that DOM-mediated dark aging processes are mainly driven by the rearrangement of DOM binding sites with Hg(II), but not the formation of mercury sulfide nanoparticles (HgSNP). The abundant but weaker RO/N (carboxyl and amino) Hg(II)-binding sites are replaced with stronger RSH (thiol) moieties towards Hg(II) binding with aging, resulting in a decrease in Hg(II) reduction. In contrast, besides reduction, DOM-mediated Hg(II) photoaging induces the formation of HgSNP, as revealed by LC-ICP-MS, which in turn decreases the microbial methylation potential of Hg(II). These findings help better understand and predict the kinetic characteristics of Hg(II) reactivity and its influence on Hg cycle within natural aquatic 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.

Interactions between dissolved organic matter and perfluoroalkyl acids in natural rivers and lakes: A case study of the northwest of Taihu Lake Basin, China

Understanding the interactions between dissolved organic matter (DOM) and perfluoroalkyl acids (PFAAs) is essential for predicting the distribution, transport, and fate of PFAAs in aquatic environments. Based on field investigations in the northwest of Taihu Lake Basin combined with laboratory experiments, we obtained DOM and PFAA concentrations as well as compositions and investigated key factors of DOM affecting PFAA variability and capture of PFAAs by DOM. Results indicated that the total concentrations of PFAAs were 73.4–689 ng/L in surface water and that PFAAs were dominated by C3–7 perfluoroalkyl carboxylic acids and perfluorooctane sulfonic acid. The main components of DOM included tyrosine-, fulvic-, and tryptophan-like substances. The Mantel test revealed a significant positive correlation between DOM and PFAAs (P = 0.0001). Fulvic-like substances were identified as the most crucial factors affecting PFAA variability. The laboratory experiments revealed that DOM can spontaneously aggregate into a microgel. Furthermore, 19.1–50.9% of PFAAs, DOM characteristic peaks, and several metals (Ca, Mg, Cu, and Fe) can be removed during aggregation, indicating the capacity of DOM binding organic/inorganic substances. The fulvic-like substances were more effectively removed than the protein-like substances. The distribution coefficients of all PFAAs except perfluorohexanoic acid significantly correlated with their perfluorinated carbon numbers (r = 0.975, p<0.001). Our results provided insights into the interactions between DOM and PFAAs, improving the understanding of the distribution, transport, and fate of PFAAs in aquatic environments.

Insight into interactions of polystyrene microplastics with different types and compositions of dissolved organic matter

Microplastics (MPs), as newly emerging pollutants, may interact with dissolved organic matter (DOM) widely present in the environment after entering the environment, thereby influencing the migration and transformation of MPs. The interaction characteristics and mechanism between DOM and MPs are restricted by many factors, and the current mechanism remains unclear. Thus, we explored the combination of MP with different types and compositions of DOM (fulvic acid (FA) and humic acid (HA)). Adsorption experiments revealed that MP has high adsorption affinity for all four DOMs, particularly FA. Meanwhile, the affinity of MP-DOM was also examined using excitation–emission matrix (EEM) analyses and fluorescence quenching method (excitation emission matrix-parallel factor analysis (EEM-PARAFAC)). Aromatic substances and hydrophobic substances dominate all DOM samples. For all DOM types tested, the quenching curve varies considerably with the type and compositions of DOM. In addition, three fluorescent components exhibited significant fluorescence quenching over time. The interaction mechanism of MPs and DOM at the molecular level was further elucidated by utilizing two-dimensional (2D) Fourier transformation infrared (FTIR) correlation spectroscopy (COS) analysis, which revealed that the oxygen-containing functional group in MPs was the most preferred DOM binding structure. This work was facilitated to explore the environmental behavior of MPs and formation of secondary MPs under natural conditions.

Elevated temperature altered the binding sequence of Cd with DOM in arable soils

Dissolved organic matter (DOM) is one of the most active soil components, which plays pivotal roles in the migration and fate of heavy metals in soils. The interactions of heavy metals with DOM are controlled by the structure and properties of DOM. The changes of temperature have a significant effect on the content and composition of DOM and thus may affect the binding nature of heavy metals with DOM. In the current study, we conducted a 180-d incubation experiment with an arable soil at temperatures of 15, 30 and 45 °C. Fluorescence spectroscopy was used to examine the composition of DOM and two-dimensional correlation spectroscopy was applied to determine the binding intensity and sequence between cadmium (Cd) with DOM. Two humic-like substances (C1, C3) and a protein-like substance (C2) were identified from soil DOM. Elevated temperature changed the characteristic and structure of DOM. The humification degree and aromaticity of DOM increased from 15 °C to 30 °C but decreased at high temperature (45 °C). The alterations in temperature exert no impact on the type of organic functional groups in DOM binding with Cd. However, elevated temperature changed the binding sequence of Cd with DOM fractions. Polysaccharide, phenolic, and aromatic groups exhibited the fastest response to Cd at 15, 30, and 45 °C, respectively. These observations would provide a better understanding on the environmental behavior of Cd in arable soils under the context of global warming.

Enhancement of algal growth by Mg2+ released from anaerobic digestion effluent of aquatic macrophytes through photolysis

Anaerobic digestion effluent (ADE) from aquatic macrophytes (Egeria densa, Elodea nuttallii, Ceratophyllum demersum and Potamogeton maackianus) contains insufficient available magnesium ions (Mg2+) to achieve maximum algal yield and nutrient removal, although Mg concentrations are not scarce at 6–10 mg L−1. Unavailable Mg2+ may be bound into complexes with dissolved organic matter (DOM). We determined the effects of ADE exposure to ultraviolet C (UVC), and degradation of DOM, on Mg availability for growth of Chlorella sorokiniana. Molecular sizes of DOM binding Mg2+ were identified with high-performance size-exclusion chromatography. The results demonstrated that 3 h exposure to UVC can decompose DOM, and release sufficient amounts of available Mg2+, i.e. 0.09 mg from 1 mg of dissolved organic carbon, thus enhancing algal yield and nutrient removal. Almost 50 % of Mg in the ADE was bound by DOM with a molecular size of 400–1170 Da as organic complexes, and the remaining Mg was bound by DOM of < 240 Da and/or Mg2+ and inorganic Mg complexes.

Nickel Binding Affinity with Size-Fractioned Sediment Dissolved and Particulate Organic Matter and Correlation with Optical Indicators

In rivers, the distribution and reactivity of heavy metals (HMs) are affected by their binding affinity with sediment dissolved organic matter (DOM) and particulate organic matter (POM). The HM-OM binding affinity affected by the interaction between DOM and POM is not well studied. This study investigated the Ni binding affinity to size-fractioned overlaying water DOM and alkaline extracted sediment POM solution (AEOM). The DOM/AEOM filtrates (&lt;0.45 μm) were sequentially separated into five nominal molecular weight (MW) solutions. The AEOM optical indicators had lower autochthonous, higher terrestrial sources, and lower aromaticity than the DOM. The Ni mass (72.3 ± 6.4%) was primarily distributed in the low molecular weight DOM (&lt;1 kDa), whereas the Ni (93.5 ± 0.4%) and organic carbon (OC) mass (85.3 ± 1.0%) were predominantly distributed in the high molecular weight AEOM. The Ni and DOM binding affinity, ([Ni]/[DOC])DOM ratio ranging from 0.76 to 27.32 μmol/g-C, was significantly higher than the ([Ni]/[DOC])AEOM ratios, which ranged from 0.64 to 2.64 μmol/g-C. The ([Ni]/[DOC])AEOM ratio correlated significantly with the selected optical indicators (r = 0.87–0.92, p &lt; 0.001), but the ([Ni]/[DOC])DOM ratio correlated weakly with the optical indicators (r = 0.13–0.40, p &gt; 0.05). In the present study, the Ni binding affinity with size-fractioned DOM/AEOM agrees with the hypothesis of the DOM and POM exchange conceptual model in sediment. The POM underwent a hydrolysis/oxidation process; hence, AEOM had a high molecular weight and stable chemical composition and structure. The Ni mainly attached to the high molecular weight AEOM and the ([Ni]/[DOC])AEOM ratios had a strong correlation with the AEOM optical indicators. In contrast, DOM had a high ([Ni]/[DOC])DOM ratio in low molecular weight DOM.

Acid-base properties of dissolved organic matter extracted from the marine environment

Marine dissolved organic matter (DOM) plays a key role in the current and future global carbon cycle, which supports life on Earth. Trace metals such as iron, an essential micronutrient, compete with protons and major ions for the binding to DOM. These competitive effects and the DOM binding capacity are related to the DOM acid-base properties, which also influence DOM transport and reactivity in marine waters. Here we present the results of a complete set of acid-base titration experiments of a pre-concentrated marine DOM sample in the range 0.01 ≤ I ≤ 0.7 M and 3 ≤ pH ≤ 10. We characterize the obtained proton binding curves using a combination of the non-ideal competitive adsorption (NICA) isotherm and Donnan electrostatic model. Within the main chemical groups of marine DOM, the carboxylic distribution was accurately characterized from the obtained data (QmaxH, 1=2.52 mol·kg−1, logk¯H,1 = 3.26, m1 = 0.69 and b = 0.70). This carboxylic mode was found to be less acidic and more homogeneous than a generic fulvic acid, but the differences are consistent with the reported variability of fulvic acids of freshwater and terrestrial origin. We find that changes in temperature (down to 5.5 °C), and the presence of calcium or magnesium (at 0.01 M) resulted in no significant modification of the proton ion binding curves obtained at 25 °C and 0.7 or 0.1 M ionic strength, respectively. We demonstrate the relevance of proton binding parameters for the modelling of the system iron/marine DOM throughout a wide range of salinity and acidity conditions in the context of different future ocean scenarios.

Regional-scale investigation of dissolved organic matter and lead binding in a large impacted lake with a focus on environmental risk assessment

Environmental risk assessment (ERA) increasingly relies on speciation modeling of bioavailability. Heavy metals are the most prevalent pollutants globally, and dissolved organic matter (DOM) plays an important role in speciation and bioavailability of heavy metals. Due to the variation of DOM properties in natural aquatic systems, improvements to the standard one-size-fits-all approach to modeling metal-DOM interactions are needed for ERA. In this study, we investigate variations in DOM and lead (Pb)-DOM binding in Lake Tai (Taihu), a large, impacted lake in eastern China that is characterized by a complex drainage network and is an important water resource at a regional level, and we assess implications of our findings within the context of ERA needs. In our study, DOM in water samples collected from across the 2,400 km2 area of Taihu was characterized using three-dimensional excitation-emission matrix and synchronous fluorescence spectroscopy spectra, the latter being used to calculate conditional stability constants for metal binding. Parallel factor analysis and peak picking were used to assess contributions of protein- and humic-like components of DOM, and fluorescence indices indicative of diagenetic processes were calculated. These quantities calculated from spectroscopic studies, in addition to water quality parameters, were analyzed by bivariate and multivariate analysis. Results show that different DOM components are highly variable across different regions of Taihu, and bivariate and multivariate analyses confirm that water quality and DOM characterization parameters are strongly interrelated. This reflects the different inputs, diagenetic and transport processes across the large expanse of Taihu. We find that the conditional stability constant of Pb-DOM binding is strongly affected by the water chemical properties and composition of DOM, though the conditional stability constant is not itself a parameter that differentiates lake water properties in different regions of the lake. The variability of DOM composition and Pb-DOM binding strength across Taihu is consistent with prior findings that a one-size-fits-all approach to metal-DOM binding may lead to inaccuracies in commonly used speciation models, and therefore such generalized approaches need improvement for regional-level ERA in complex watersheds. The approach taken here to obtain site-specific metal-DOM conditional stability constants for use in increasing the accuracy of speciation modeling is fit-for-purpose for ERA applications at regional levels because the approach is relatively simple, inexpensive, and amenable to high throughput analysis.

Increased soil pH and dissolved organic matter after a decade of organic fertilizer application mitigates copper and zinc availability despite contamination

Long-term organic fertilizer (OF) application on agricultural soils is known to induce soil Cu and Zn contamination, along with pH and organic matter changes, which in turn alter the soil Cu and Zn availability. Our study was aimed at assessing Cu and Zn availability in long-term OF-amended soils by distinguishing the importance of increased contamination levels versus pH and organic matter changes in soil. Seventy-four soil samples were collected over time from fields corresponding to three soil types upon which no, mineral, or organic fertilization had been applied over a decade, and thus exhibited a gradient of Cu and Zn contamination, pH, and organic matter concentration. Soil Cu and Zn contamination (i.e. total and DTPA-extractable Cu and Zn concentration), soil solution chemistry (i.e. pH and dissolved organic matter concentration and aromaticity) and Cu and Zn availability (i.e. total concentration and free ionic activity in solution and DGT-available concentration in soil) levels were measured. The Windermere humic aqueous model (WHAM) was used to estimate Zn2+ activity and dissolved organic matter (DOM) binding properties in soil solution. Regardless of the soil type, organic fertilization increased Cu and Zn contamination in soil, in addition to the pH and the DOM concentration, aromaticity and binding properties in soil solution. The pH increase prompted a decrease in the total Zn concentration and Zn2+ activity in soil solution. The concomitant pH increase and DOM concentration, aromaticity and binding properties boosted the total Cu concentration but decreased the Cu2+ activity in soil solution. DGT-available Cu and Zn varied very little between the three fertilization modalities. Our results suggest that pH and DOM changes were able to regulate Cu and Zn availability in long-term OF amended soils by exerting a protective effect that offset the concomitant increase in soil Cu and Zn contamination.

Parallel faction analysis combined with two-dimensional correlation spectroscopy reveal the characteristics of mercury-composting-derived dissolved organic matter interactions

Dissolved organic matter (DOM) is regarded as the environmentally friendly substance. Strong complexes could be formed between DOM and heavy metals. Thus, the distribution, bioavailability, toxicity, and fate of heavy metals could be controlled in the environment. The widely spread method for characterizing metal-organic interactions is restricted to combine parallel faction analysis (PARAFAC) with the complexation model. However, a DOM PARAFAC component always contains two or more peaks. Therefore, the traditional method cannot reveal the inner changes of PARAFAC components or whether all the DOM peaks in one PARAFAC component are bound with metal during the metal-organic binding process. In this work, two-dimensional correlation spectroscopy (2DCOS) combined with PARAFAC and the complexation model were employed to reveal the binding speed and ability of different fluorescent peaks from DOM PARAFAC components during the binding process of mercury (Hg2+) to DOM. The results in this study showed that during the Hg2+-DOM binding process, fluorescent peaks in tryptophan-like component all presented Hg2+-binding ability. However, only humic-like component ligands showed Hg2+-binding ability. With these promising results, the true Hg2+ binding rate and ability of different DOM ligands can be revealed, which is helpful for addressing environmental pollution.

New insight into chemical changes between dissolved organic matter and environmental nano-CuO pollutants binding experiment using multi-spectroscopic techniques

In this work, the copper oxide nanoparticles (nano-CuO) binding characteristics to dissolved organic matter (DOM) fractions was investigated based on three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, parallel factor analysis (PARAFAC) and two dimensional correlation spectroscopy (2D-COS). According to the results, the three fluorescence components were obtained from EEM-PARAFAC; furthermore, their related expressed fluorescence intensity reduced with the increase of nano-CuO concentrations. According to the 2D-COS combined with the spectra of synchronous fluorescence, the humic-like fraction fluorescence was more susceptible than protein-like fraction, while the fluorescence changes sequentially occurred in the order as below: protein-like fraction < humic-like fraction. According to two-dimensional Fourier Transformation Infrared correlation spectroscopy (2D-COS-FTIR), DOM's the structural change sequence by nano-CuO binding was in the order as below: 1432 > 1057 > 1600 > 842 > 913 > 1300 cm−1. To be more detailed, DOM binding to nano-CuO's sequential order is COO− antisymmetric stretching > polysaccharide C-O > amide I C-O > aromatic CH in cellulose > C-O stretching of phenolic and deformation of OH. Hetero 2D-COS maps further revealed the close association between the aromatic functional groups and humic-like substances, and between carboxylic groups and protein-like substances. The findings would be beneficial to understand the mechanism of the superior potential of 2D hetero spectral correlation spectroscopy in studying complex interactions with DOM at the molecular level in the soil environment.

Molecular fractionation of dissolved organic matter on ferrihydrite: effects of dissolved cations

Environmental contextCarbon sequestration and dynamics are influenced by adsorptive fractionation of dissolved organic matter (DOM) on minerals. We found that the molecular fractionation of DOM on ferrihydrite was highly dependent on the presence of Na, Ca and Cu ions in water. These results advance our mechanistic understanding of the dynamic behaviour of DOM, and contribute to predicting carbon cycling and contaminant behaviour in the natural environment. AbstractThe adsorptive fractionation of dissolved organic matter (DOM) at the ferrihydrite and water interface is a key geochemical process controlling DOM compositions and reactivity, thus affecting carbon cycling and contaminant behaviour in the environment. However, the effects of cations on DOM fractionation and the underlying mechanisms are poorly understood. In this study, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with spectroscopic methods were employed to investigate molecular fractionation of DOM on ferrihydrite under different cations in the background electrolytes, including Na, Ca, and Cu ions. The results indicated that DOM fractionation was influenced by the combined effects of cation type, intrinsic molecular property, and extent of DOM adsorption. DOM adsorption on ferrihydrite exhibited the strongest and the weakest fractionation under Na and Ca background electrolytes, respectively. Both Ca and Cu background electrolytes reduced the adsorption of highly unsaturated and phenolic/polyphenolic molecules with high molecular weight and number of O atoms. In addition to the molecular acidity, the complexation of Ca and Cu ions to DOM binding sites and the coagulation effect of divalent cations may affect molecular fractionation. Additionally, DOM fractionation was enhanced with increasing DOM adsorption. Our results contribute to predicting carbon cycling and contaminant behaviour in the natural environment.

Soil dissolved organic matter affects mercury immobilization by biogenic selenium nanoparticles

Molecular weight (MW) heterogeneity is a fundamental property of dissolved organic matter (DOM) in soil, which has been demonstrated to influence the binding behaviour between DOM and engineered nanoparticles. In the present study, DOM, extracted from black soil, was dialyzed into four fractions: above 10,000 Da, 3500–10,000 Da, 1000–3500 Da and 100–1000 Da. Homoaggregation and fluorescence quenching titration of selenium nanoparticles (SeNPs) was examined in the presence of the different DOM fractions, as well as the consequences for immobilization of elemental mercury. It was found that the intermediate MW fraction (3500–10,000 Da) rather than the high MW DOM fraction was likely to adsorb to SeNPs. Generally, low MW DOM was expected to adsorb initially due to faster diffusion and these compounds would be displaced by high MW DOM over longer time period. However, the electrostatic barrier imparted by adsorbed DOM limited such displacement, leading to preferential adsorption of the intermediate MW fraction over the high MW fraction. Adsorbed DOM fractions, especially that of intermediate MW, enhanced the stability of SeNPs which favoured immobilization of elemental mercury. These findings show that MW exerts an important impact on DOM binding with SeNPs which, in consequence, governs the fate of SeNPs and mercury bioremediation performance.

Influence of heavy metal ions on the spectra and charge characteristics of DOM of municipal sewage secondary effluent.

The spectral and charged characteristics of dissolved organic matter (DOM) in municipal sewage secondary effluent influenced by heavy metal ions were studied by three-dimensional fluorescence spectroscopy, ultraviolet spectrometry, etc. As the Cu(II) concentration increased, the fluorescence intensity of the DOM's fluorescence peak reduced. When the Cu(II) concentration was 100 μmol/L, the fluorescence intensity of the humic-like acid in the DOM reduced by 19.5%-27.6%. However, there was no obvious change in the fluorescence intensity when Cd(II) was added. According to the modified Stern-Volmer equation, the conditional stability constant lgK and the proportion of the fluorescent functional groups of the DOM binding with Cu(II) were 2.19-2.69 and 16%-48%, respectively. The UV253/UV203 value changed little with the additional dosage of metal ions below 10 μmol/L, which increased as the concentration of Cu(II) or Pb(II) increased from 10-100 μmol/L. As the metal concentrations increase, the absolute values of the Zeta potential and the particle sizes of the DOM basically increased. The results showed that Cu(II) had the strongest binding ability to the groups that emitted fluorescence in the secondary effluent DOM compared to Pb(II) and Cd(II).

Spectroscopic study of interactions of lead (II) ions with dissolved organic matter: Evidence of preferential engagement of carboxylic groups

The speciation, bioavailability and transport of Pb(II) in the environment are strongly affected by dissolved organic matter (DOM). Despite the importance of these interactions, the nature of Pb(II)-DOM binding is insufficiently attested. This study addressed this deficiency using the method of differential absorbance spectroscopy in combination with the non-ideal competitive adsorption (NICA)-Donnan model. Differential absorbance data allowed quantifying the interactions between Pb(II) and DOM in a wide range of pH values, ionic strengths and Pb(II) concentrations at an environmentally relevant DOM concentration (5mgL−1). Changes of the slopes of the log-transformed absorbance spectra of DOM in the range of wavelength 242–262 and 350–400nm were found to be predictive of the extent of Pb(II) bound by DOM carboxylic groups and of the total amount of DOM-bound Pb(II), respectively. The results also demonstrated the preferential involvement of DOM carboxylic groups in Pb(II) binding. The spectroscopic data allowed optimizing selected Pb(II)-DOM complexation constants used in the NICA-Donnan Model. This resulted in a markedly improved performance of that model when it was applied to interpret previously published Pb(II)-fulvic acid datasets.

Parameterizing the binding properties of dissolved organic matter with default values skews the prediction of copper solution speciation and ecotoxicity in soil.

Parameterizing speciation models by setting the percentage of dissolved organic matter (DOM) that is reactive (% r-DOM) toward metal cations at a single 65% default value is very common in predictive ecotoxicology. The authors tested this practice by comparing the free copper activity (pCu2+ = -log10 [Cu2+ ]) measured in 55 soil sample solutions with pCu2+ predicted with the Windermere humic aqueous model (WHAM) parameterized by default. Predictions of Cu toxicity to soil organisms based on measured or predicted pCu2+ were also compared. Default WHAM parameterization substantially skewed the prediction of measured pCu2+ by up to 2.7 pCu2+ units (root mean square residual = 0.75-1.3) and subsequently the prediction of Cu toxicity for microbial functions, invertebrates, and plants by up to 36%, 45%, and 59% (root mean square residuals ≤9 %, 11%, and 17%), respectively. Reparametrizing WHAM by optimizing the 2 DOM binding properties (i.e., % r-DOM and the Cu complexation constant) within a physically realistic value range much improved the prediction of measured pCu2+ (root mean square residual = 0.14-0.25). Accordingly, this WHAM parameterization successfully predicted Cu toxicity for microbial functions, invertebrates, and plants (root mean square residual ≤3.4%, 4.4%, and 5.8%, respectively). Thus, it is essential to account for the real heterogeneity in DOM binding properties for relatively accurate prediction of Cu speciation in soil solution and Cu toxic effects on soil organisms. Environ Toxicol Chem 2017;36:898-905. © 2016 SETAC.

Quantitative relationships between the adsorptivity of carbonaceous materials in soil for Pb(II) and soil organic matter content

Strong adsorptivity of manufactured carbonaceous materials (MCMs) mediates the behavior of heavy metals in soil. Laboratory-reported adsorptivity of MCMs often deviates from their actual abilities in soil, because soil organic matter (SOM) can change the adsorptive abilities of MCMs by coating dissolved organic matter (DOM) on the surface of the MCMs. It was considered that the influence of SOM on the adsorptivity of MCMs in soil follows a sequential pathway of SOM releasing DOM in soil solution and subsequent DOM binding onto MCMs, thereby altering MCM surface acidity and hence changing MCM adsorptivity for heavy metals. In this study, we first extracted DOM from ten topsoils collected over a broad region of China with a wide range of SOM. The DOM solutions were then used to load DOM onto four MCMs including activated carbon (AC), multiwalled carbon nanotube (MWCNT), and two biochars (BC400 and BC700), respectively, obtaining a total of 44 MCM-DOM complex samples with known amounts of bound DOM. These MCM-DOM complex samples were then determined for their surface acidities and adsorptive abilities for Pb(II). We found that there were significant correlations between DOM concentration and SOM content, between DOM binding onto MCMs and DOM concentration, between surface acidity of MCM-DOM complexes and DOM binding onto MCMs, as well as between Pb(II) adsorption on MCM-DOM complexes and surface acidity of MCM-DOM complexes. With understanding of these individual linear correlations, linear relationships between the Pb(II) adsorption and SOM content were established by combining individual correlations and by directly plotting the former against the latter. These relationships may be used to accurately predict the adsorptive abilities of MCMs for heavy metals in soils via simply determining SOM.