Absence Of Natural Organic Matter Research Articles

Putting advanced materials to the test: Ti3C2 MXenes alleviate the hazardous effects of the environmental pollutant benzo[a]pyrene

Advanced materials are materials that have been engineered to exhibit novel or enhanced properties that confer superior performance when compared to conventional materials. Here, we evaluated the impact of Ti3C2 MXenes, a two-dimensional (2D) material, on the adverse effects caused by polycyclic aromatic hydrocarbons. To this end, we studied benzo[a]pyrene denoted here as B[a]P as a model compound. B[a]P was found to adsorb to MXenes as evidenced by UV–Vis spectroscopy. MXenes in the presence or absence of natural organic matter (NOM) were well tolerated by zebrafish embryos. The uptake (ingestion) of MXenes by zebrafish was determined by quantifying the Ti content using inductively coupled plasma mass spectrometry (ICP-MS) while Raman confocal mapping was applied for the label-free identification of MXenes in situ in exposed zebrafish. The body burden of B[a]P was determined by gas chromatography-mass spectrometry (GC-MS). The potential impact of MXenes on B[a]P triggered aryl hydrocarbon receptor (AhR) induction was assessed by evaluating the induction of downstream genes including cyp1a, and results were validated by using the transgenic zebrafish reporter tg(cyp1a-eGFP). The potential impact of MXenes on the genotoxicity caused by B[a]P was also assessed. MXenes were shown to ameliorate AhR induction and DNA damage caused by B[a]P. This was corroborated by using the human colon-derived cell line HT-29. Taken together, MXenes were found to be non-hazardous and alleviated the adverse effects caused by B[a]P in vitro and in vivo.

Natural organic matter (NOM) can increase the uptake fluxes of three critical metals (Ga, La, Pt) in a unicellular green alga

Critical metals such as gallium, lanthanum and platinum are considered essential in a modern economy and for the required energy transition. Their relatively recent and increasing use in new technologies have led to an increase in their environmental mobility. As they reach aquatic systems, these metals can interact with organic ligands and especially Natural Organic Matter (NOM). The formation of organic complexes would be expected to reduce metal bioavailability and uptake by living cells, according to the Biotic Ligand Model (BLM). However, exceptions to this model have been determined for several critical metals in the past. The present work compared internalization kinetics of Ga, La and Pt in the green alga Chlamydomonas reinhardtii in the presence of NOMs from different origins: humic and fulvic acids from Suwannee River as well as NOMs from Ontario (Bannister Lake and Luther Marsh). Complexation was determined using a partial ultrafiltration method allowing for a normalization of data based on speciation to compare all conditions based on the concentration of the metal that was not bound to NOM. While internalization metal fluxes varied greatly from one NOM source to the other, uptake was almost always significantly higher than expected based on metal speciation. Quite often, metal internalization fluxes were even significantly increased in the presence of NOM, for the same total metal exposure concentration. For instance, Pt internalization was twice greater in the presence of Bannister Lake NOM than it was in the absence of NOM. The assumption that such exceptions could be explained by NOM characteristics was contradicted by the variable results from one metal to another. To further explore this phenomenon, internalization mechanisms for these individual metals need to be elucidated. This is a necessary step to accurately estimate the risk posed by the presence of these metals in humic aquatic systems.

Exacerbated interfacial impacts of nanoplastics and 6:2 chlorinated polyfluorinated ether sulfonate by natural organic matter in adult zebrafish: Evidence through histopathology, gut microbiota, and transcriptomic analysis

Nanoplastics (NPs) interact with cooccurring chemicals and natural organic matter (NOM) in the environment, forming complexes that can change their bioavailability and interfacial toxicity in aquatic organisms. This study aims to elucidate the single and combined impacts of 21-day chronic exposure to low levels of polystyrene NPs (size 80 nm) at 1 mg/L and 6:2 chlorinated polyfluorinated ether sulfonate (Cl-PFAES or F53B) at 200 μg/L in the presence and absence of NOM (humic acid-HA and bovine serum albumin-BSA at 10 mg/L) in adult zebrafish (Danio rerio). Our findings through multiple bioassays, revealed that the mixture group (M), comprising of NPs, F53B, HA, and BSA, caused a higher level of toxicity compared to the single NPs (AN), single F53B (AF), and combined NPs+F53B (ANF) groups. The mixture exposure caused the highest level of vacuolization and nuclear condensation in hepatocytes, and most of the intestinal villi were fused and highly reduced in villi length and crypt depth. Further, the T-AOC levels were significantly lower (p < 0.05), while the MDA levels in the liver and intestine were significantly higher (p < 0.05) in the M group with downregulation of nfkbiaa, while upregulation of prkcda, csf1ra, and il1b apoptosis genes in the liver. Pairwise comparison of gut microbiota showed significantly higher (p < 0.05) abundances of various genera in the M group, including Gordonia, Methylobacterium, Tundrisphaera, GKS98, Pedomicrobium, Clostridium, Candidatus and Anaerobacillus, as well as higher abundance of genera including pathogenic strains, while control group showed higher abundance of probiotic genus ZOR0006 than exposed group (p < 0.01). The transcriptomic analysis revealed highest number of DEGs in the M group (2815), followed by the AN group (506) and ANF group (206) with the activation of relaxin signaling pathway-RSP (slc9a1, slc9a2) and AMP-activated protein kinase (AMPK) pathway (plin1), and suppression of the toll-like receptor (TLR) pathway (tlr4a, tlr2, tlr1), cytokine-cytokine receptor interaction (CCRI) pathway (tnfb, il21r1, il21, ifng1), and peroxisome proliferator-activated receptors (PPAR) pathway (pfkfb3). Overall, toxicity in the M group was higher, indicating that the HA and BSA elevated the interfacial impacts of NPs and F53B in adult zebrafish after chronic environmentally relevant exposure, implying the revisitation of the critical interaction of NOM with co-occurring chemicals and associated impacts

Heteroaggregation kinetics of oppositely charged nanoplastics in aquatic environments: Effects of particle ratio, solution chemistry, and interaction sequence

Interactions between positively charged amino-modified (APS) and negatively charged bare (BPS) polystyrene nanoplastics may cause heteroaggregation in aquatic environments. This study investigated the effects of particle concentration ratio, solution chemistry [electrolytes, pH, and natural organic matter (NOM)], and interaction sequence on their heteroaggregation kinetics. In the absence of electrolytes and NOM, the APS/BPS ratio for attaining maximum heteroaggregation rate (khetero) increased from APS/BPS= 3/7 to APS/BPS= 1/1 as pH increased from 4 to 10, indicating that electrostatic interactions dominated heteroaggregation. In the absence of NOM, khetero ranked APS/BPS= 2/3 > APS/BPS= 1/1 > APS/BPS= 3/2. Colloidal stability decreased linearly as pH increased from 4 to 8 at APS/BPS= 1/1, while diffusion-limited heteroaggregation persisted at pH 10. In NaCl solution, humic acid (HA) retarded heteroaggregation more effectively than sodium alginate (SA) via steric hindrance and weakening electrostatic interactions, following the modified Derjaguin-Landau-Verwey-Overbeek (MDLVO) theory. Compared with simultaneous interactions among APS, BPS, NaCl, and NOM, the NOM retardation effects on heteroaggregation weakened if delaying its interaction with others. In CaCl2 solution, the effects of NOM on heteroaggregation depended on counterbalance among charge screening, steric hindrance, and calcium bridging. These findings highlight the important role of heteroaggregation between oppositely charged nanoplastics on their fate and transport in aquatic environments.

Role of Ripening in the Deposition of Fragments: The Case of Micro- and Nanoplastics.

Particulate contaminants, such as microplastics (1 μm to 5 mm) and nanoplastics (<1 μm), are disseminated in many terrestrial environments. However, it is still unclear how particles' properties drive their mobility through soils and aquifers due to (i) poor environmental relevance of the model particles that are studied (e.g., spherical and monodisperse) and (ii) the use of packed bed experiments which do not allow a direct observation of deposition dynamics. Using transparent 2D porous media, this study analyzes deposition dynamics of rough polystyrene fragments with irregular shapes and with a size continuum (≈10 nm to 5 μm). Using in situ and ex situ measurements, particle deposition as a function of size was monitored over time under repulsive conditions. In the absence of natural organic matter (NOM), micrometric particles rapidly deposit and promote the physical interception of smaller nanoparticles by creating local porous roughness or obstacles. In the presence of NOM, differences according to particle size were no longer observed, and all fragments were more prone to being re-entrained, thereby limiting the growth of deposits. This work demonstrates the importance of pore surface roughness and porosity of the pore surface for the deposition of colloidal particles, such as microplastics and nanoplastics, under repulsive conditions.

Impact of organic matter of different origins on lanthanum speciation, bioavailability and toxicity toward a green alga

Natural dissolved organic matter (DOM) is a heterogeneous mixture of a variety of organic compounds, with a great importance for the environmental fate of metals and their ecotoxicity. However, its complex nature and variable composition make the understanding of its role a challenge. Lanthanum (La) has a strong affinity for DOM and is one of the rare earth elements that is widely used in many electronic and green technologies, and for which the demand may potentially increase for the foreseeable future. The present study examines the links between the optical and chemical properties of organic matter and its influence on the bioavailability and toxicity of La toward the green microalga Chlorella fusca. A total of four DOMs, two natural organic matter samples from Ontario (Luther Marsh and Bannister Lake) and two Suwannee River fulvic and humic acids, were characterized by absorbance and fluorescence spectroscopy as well as by asymmetrical flow field-flow fractionation. These suggest that Luther Marsh and the Suwannee River humic acid have higher molecular weight and are more aromatic, compared to the other two DOMs. The concentrations of free metal ion La3+ were measured by an ion exchange technique and a partial ultrafiltration method, and related to biological response. Toxicity tests over 96 h at pH = 5.0 were separately conducted with and without 3 mg C·L−1 of each DOM. All DOM samples reduced La bioavailability but as opposed to what can be expected based on the Biotic Ligand Model, the presence of DOM exacerbated the toxicity of La and its accumulation in algal cells when only the free La3+ ion concentration was considered. These results indicate that the role of natural organic matter in modulating metal bioavailability remains to be deciphered.

Mercury Removal from Contaminated Water by Wood-Based Biochar Depends on Natural Organic Matter and Ionic Composition.

Biochars can remove potentially toxic elements, such as inorganic mercury [Hg(II)] from contaminated waters. However, their performance in complex water matrices is rarely investigated, and the combined roles of natural organic matter (NOM) and ionic composition in the removal of Hg(II) by biochar remain unclear. Here, we investigate the influence of NOM and major ions such as chloride (Cl–), nitrate (NO3–), calcium (Ca2+), and sodium (Na+) on Hg(II) removal by a wood-based biochar (SWP700). Multiple sorption sites containing sulfur (S) were located within the porous SWP700. In the absence of NOM, Hg(II) removal was driven by these sites. Ca2+ bridging was important in enhancing removal of negatively charged Hg(II)-chloro complexes. In the presence of NOM, formation of soluble Hg-NOM complexes (as seen from speciation calculations), which have limited access to biochar pores, suppressed Hg(II) removal, but Cl– and Ca2+ could still facilitate it. The ability of Ca2+ to aggregate NOM, including Hg-NOM complexes, promoted Hg(II) removal from the dissolved fraction (<0.45 μm). Hg(II) removal in the presence of Cl– followed a stepwise mechanism. Weakly bound oxygen functional groups in NOM were outcompeted by Cl–, forming smaller-sized Hg(II)-chloro complexes, which could access additional intraparticle sorption sites. Therein, Cl– was outcompeted by S, which finally immobilized Hg(II) in SWP700 as confirmed by extended X-ray absorption fine structure spectroscopy. We conclude that in NOM containing oxic waters, with relatively high molar ratios of Cl–: NOM and Ca2+: NOM, Hg(II) removal can still be effective with SWP700.

Facile synthesis of graphene wool doped with oleylamine-capped silver nanoparticles (GW-\u03b1AgNPs) for water treatment applications

The facile synthesis of graphene wool doped with oleylamine-capped silver nanoparticles (GW-αAgNP) was achieved in this study. The effect of concentration, pH, temperature and natural organic matter (NOM) on the adsorption of a human carcinogen (benzo(a)pyrene, BaP) was evaluated using the doped graphene wool adsorbent. Furthermore, the antibacterial potential of GW-αAgNP against selected drug-resistant Gram-negative and Gram-positive bacteria strains was evaluated. Isotherm data revealed that adsorption of BaP by GW-αAgNP was best described by a multilayer adsorption mechanism predicted by Freundlich model with least ERRSQ < 0.79. The doping of graphene wool with hydrophobic AgNPs coated with functional moieties significantly increased the maximum adsorption capacity of GW-αAgNP over GW based on the qmax and qm predicted by Langmuir and Sips models. π-π interactions contributed to sorbent-sorbate interaction, due to the presence of delocalized electrons. GW-αAgNP-BaP interaction is a spontaneous exothermic process (negative Delta H^circ and Delta G), with better removal efficiency in the absence of natural organic matter (NOM). While GW is more feasible with higher maximum adsorption capacity (qm) at elevated temperatures, GW-αAgNP adsorption capacity and efficiency is best at ambient temperature, in the absence of natural organic matter (NOM), and preferable in terms of energy demands and process economics. GW-αAgNP significantly inhibited the growth of Gram-negative Pseudomonas aeruginosa and Gram-positive Bacillus subtilis strains, at 1000 mg/L dosage in preliminary tests, which provides the rationale for future evaluation of this hybrid material as a smart solution to chemical and microbiological water pollution.

Equilibrium calculations of iron speciation and apparent iron solubility in the Celtic Sea at ambient seawater pH using the NICA-Donnan model

We used a combined ion pairing - organic matter speciation model (NICA-Donnan) to predict the organic complexation of iron (Fe) at ambient pH and temperature in the Celtic Sea. We optimized our model by direct comparison with Fe speciation determined by Adsorptive Cathodic Stripping Voltammetry using the added Fe-binding ligand 1-nitroso-2-naphthol (HNN) in the presence and absence of natural organic matter. We compared determined Fe speciation with simulated titrations obtained via application of the NICA-Donnan model with four different NICA parameter sets representing a range of binding site strengths and heterogeneities. We tested the assumption that binding sites scale to dissolved organic carbon (DOC) concentrations in marine waters. We found that a constant low DOC concentration resulted in an improved fit of our titration data to the simulated titrations, suggesting that inputs of autochthonous marine DOM may not increase the heterogeneity or concentrations of Fe binding sites. Using the optimal parameter set, we calculated pFe(III)´ (−log(∑Fe(OH)i3−i)) and apparent Fe(III) solubility (SFe(III)app) at ambient pH and temperature in the water column of the Celtic Sea. SFe(III)app was defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to DOM formed at a free Fe (Fe3+) concentration equal to the limiting solubility of Fe hydroxide (Fe(OH)3(s)). SFe(III)app was within range of the determined dissolved Fe concentrations observed after winter mixing on the shelf and in waters >1500 m depth at our most offshore stations. Our study supports the hypothesis that the ocean dissolved Fe inventory is controlled by the interplay between Fe solubility and Fe binding by organic matter, although the overall number of metal binding sites in the marine environment may not be directly scalable to DOC concentrations.

Exposure of nanoplastics to freeze-thaw leads to aggregation and reduced transport in model groundwater environments

Despite plastic pollution being a significant environmental concern, the impact of environmental conditions such as temperature cycling on the fate of nanoplastics in cold climates remains unknown. To better understand nanoplastic mobility in subsurface environments following freezing and thawing cycles, the transport of 28 nm polystyrene nanoplastics exposed to either constant (10°C) temperature or freeze-thaw (FT) cycles (-10°C to 10°C) was investigated in saturated quartz sand. The stability and transport of nanoplastic suspensions were examined both in the presence and absence of natural organic matter (NOM) over a range of ionic strengths (3-100 mM NaCl). Exposure to 10 FT cycles consistently led to significant aggregation and reduced mobility compared to nanoplastics held at 10°C, especially at low ionic strengths in the absence of NOM. While NOM increased nanoplastic mobility, it did not prevent the aggregation of nanoplastics exposed to FT. We compare our findings with existing literature and show that nanoplastics will largely aggregate and associate with soils rather than undergo long range transport in groundwater in colder climates following freezing temperatures. In fact, FT exposure leads to the formation of stable aggregates that are not prone to disaggregation. As one of the first studies to examine the coupled effect of cold temperature and NOM, this work highlights the need to account for climate and temperature changes when assessing the risks associated with nanoplastic release in aquatic systems.

Effects of natural organic matter on the photolysis of tetracycline in aquatic environment: Kinetics and mechanism

The residues of tetracycline in environment have raised increasing concern for the deleterious impact on ecological and human health. Natural organic matter (NOM), ubiquitous in natural waters, is unavoidable to encounter tetracycline, which might affect the fate of tetracycline in aquatic environment. In this study, we investigated the effect of natural organic matter (NOM) on the photolytic fate of tetracycline (TC). The photolysis kinetics of TC were evaluated with two representative NOM, tannic acid (TA) and gallic acid (GA). The presence of TA and GA obviously inhibited the removal of TC under UV irradiation with photolysis rate constant at 0.067 h−1 and 0.071 h−1, respectively, which were 32.3% and 28.3% less than that without TA and GA (0.099 h−1). Furthermore, NOM exhibited different impacts on both indirect photolysis and direct photolysis. NOM promoted the formation of hydroxyl radical, induced the generation of triplet-excited state NOM and thus greatly enhanced the indirect photolysis of TC. However, direct photolysis was almost completely inhibited by NOM via inner filter effect and interacting with TC to form ground-state complex with low photoreactive. Moreover, similar intermediates were detected in the presence and absence of NOM, indicating that NOM exhibited limited influence on the degradation pathways of TC. This study reveals the multiple roles of NOM on tetracycline photolysis, contributing to better understand the photolytic fate of antibiotics in natural waters.

Removal of heavy metals from water using electrospun polyelectrolyte complex fiber mats

This study investigated the removal of heavy metals from water using electrospun polyelectrolyte (PE) complex fibers of polyacrylic acid (PAA) and polyallylamine hydrochloride (PAH). PE fiber mats were fabricated under various electrospinning operating conditions to optimize fiber size and stability in aqueous solution. The stable fiber mats were evaluated for their efficiency in removing heavy metals in synthetic metal solutions. The effect of water matrix on heavy metal removal using the PAA/PAH fiber mats was probed by comparing metal removals in the presence and absence of natural organic matter (NOM). The fiber mats exhibited approximately 63 %, 42 %, and 21 % removals of lead (Pb), cadmium (Cd), and copper (Cu), respectively in synthetic metal solutions at pH 3.4. Furthermore, approximately 70 %, 98 %, and 92 % removals of Pb, Cd, and Cu, respectively were observed at a higher pH (7.4). The heavy metal removal by the PAA/PAH complex fiber mats may be attributed to the association of the metal ions with carboxylate ions from the fibers. The presence of NOM in the metal-spiked solutions resulted in higher removal of metals by the fiber mats. This can be attributed to the availability of NOM-derived carboxylic acid groups, which resulted in increased metal-carboxylate complexations. This study implies that water matrix plays an important role that must be evaluated when removing metals using PE complex fibers.

Morphology, structure, and composition of sulfidized silver nanoparticles and their aggregation dynamics in river water

The sulfidized form represents an environmentally relevant transformation state of silver nanoparticles (Ag-NPs) released into natural systems via wastewater route. However, the detailed characterization of sulfidized silver nanoparticles (S-Ag-NPs) is missing and their colloidal stability in aquatic systems is only insufficiently studied. The aim of this study was to systematically evaluate the surface properties, morphology, structure, composition, as well as aggregation dynamics of S-Ag-NPs in synthetic and natural river water. The S-Ag-NPs were prepared by sulfidation of citrate-coated silver nanoparticles (Cit-Ag-NPs). The sulfidation of Ag-NPs was accompanied by the formation of fiber-like Ag2S nano-bridges, Ag0-Ag2S core-shell structures, and hollow regions. In contrast to the published literature, the nano-bridges were thinner (2–9 nm) and longer (up to 60 nm), they formed at higher S2−/Ag molar ratio (2.041), and the formation of the core-shell structures was observed even in the absence of natural organic matter (NOM). Furthermore, we observed selective sulfidation of nanoparticles which can induce the hot spots for the release of toxic Ag+ ions. The critical coagulation concentration (CCC) of Ca2+ determined for S-Ag-NPs in reconstituted river water was 2.47 ± 0.23 mmol/L and thus higher than the CCC obtained for Cit-Ag-NPs in our earlier study revealing higher colloidal stability of S-Ag-NPs. In natural river water, S-Ag-NPs were also colloidally more stable compared to the Cit-Ag-NPs. Furthermore, the stabilizing effect of NOM was much higher for S-Ag-NPs than for Cit-Ag-NPs. For S-Ag-NPs stabilized by a low amount of citrate, we expect longer residence times in the water phase of rivers and thus higher risk for aquatic organisms. In contrast to this, the pristine Cit-Ag-NPs are expected to be accumulated faster in the sediments representing higher risk for benthic organisms. This study contributes to better understanding of environmental fate and effects of Ag-NPs released via wastewater route.

Organic Amines Enhance the Formation of Iodinated Trihalomethanes during Chlorination of Iodide-Containing Waters

The effects of organic amines (OAs) including glycine (Gly), sarcosine (Sar), and triethanolamine (Tea), representing primary, secondary, and tertiary amines, respectively, on iodinated trihalomethanes (I-THMs) formation during chlorination of iodide (I-)-containing waters were investigated. The total concentration of I-THMs formed in the co-presence of an OA and natural organic matter (NOM) was more than 3 times the sum of those formed in the presence of an OA alone and NOM alone, as OAs competed for free chlorine (FC) to form organic chloramines. Taking Gly as an example, the transformation of I- was determined. In the absence of NOM, the yields of iodate (IO3-) were 89%, 60%, and nearly 0 at [Gly]o/[FC]o = 0:1, 3:4, and 1:1, but 0, 2%, and 43% for hypoiodous acid (HOI), respectively. In the presence of NOM, as [Gly]o/[FC]o increased from 0:1 to 1:1, the yield of IO3- decreased from 66% to 0, while that of I-THMs increased from 2.9% to 16.1%. The competition of FC by OAs inhibited the oxidation of HOI to IO3-, and the formed organic chloramines can oxidize I- to HOI, thus promoting I-DBPs formation. Finally, the enhanced I-THMs formation was verified in real waters.

Factors affecting N-nitrosodimethylamine formation from poly(diallyldimethyl-ammonium chloride) degradation during chloramination.

Poly(diallyldimethylammonium chloride) (polyDADMAC) has been shown to be an important precursor of the probable human carcinogen N-nitrosodimethylamine (NDMA) when in contact with chloramine. In this study, we conducted an orthogonal experiment design to evaluate the effects of pH values, ammonia, bromide, natural organic matter (NOM) and monochloramine dosages on the formation of NDMA from polyDADMAC during chloramination. Meanwhile, single-factor experiments of pH, bromide and NOM prove the results of orthogonal experiment. The results supported that pH was the most critical factor affecting NDMA formation from polyDADMAC during chloramination, and the highest NDMA formation from polyDADMAC occurred at pH near 7 due to released DMA from polyDADMAC degradation and the critical importance of low concentrations of dichloramine in water. In the presence of excess bromide, the NDMA formation was enhanced significantly at all different pH values owing to bromochloramine, which has higher electronegativity of the brominated nitrogen atom than monochloramine or dichloramine. The NDMA formation from polyDADMAC in the presence of NOM was 41.7% lower than NDMA formation in the absence of NOM. The overwhelming majority of NDMA formation from polyDADMAC under simulated conditions was lower than the current advisory levels (i.e. 9 ng l−1 in Ontario, 10 ng l−1 in California).

Impact of chlorination on silver elution from ceramic water filters

Applying silver nanoparticles (nAg) or silver nitrate (AgNO3) to ceramic water filters improves microbiological efficacy, reduces biofilm formation, and protects stored water from recontamination. A challenge in ceramic filter production is adding sufficient silver to achieve these goals without exceeding the maximum recommended silver concentration in drinking water. Silver release is affected by silver type, application method, and influent water chemistry. Despite a lack of data, there is an assumption that chlorinated water should not be used as influent water because it may increase silver elution. Thus, the objective of this work was to systematically evaluate the impact of chlorinated water (0–4 mg/L free chlorine residual, FCR) on silver release from ceramic filter disks painted with casein-coated nAg, painted with AgNO3, or containing fired-in nAg over a range of ionic strength (IS = 0–10 mM as NaNO3) in the presence or absence of natural organic matter (NOM). Influent deionized water containing chlorine increased silver release 2–5-fold compared to controls. However, this effect of chlorine was mitigated at higher IS (≥1 mM) or in the presence of NOM (3 mg C/L). For filter disks painted with nAg or AgNO3, silver release increased with increasing IS (with or without chlorine), and effluent concentrations remained above the World Health Organization (WHO) guideline of 0.1 mg/L even after 30 h (80 pore volumes, PVs) of flow with a background solution of 10 mM NaNO3. Silver speciation (nAg vs. Ag+) was monitored in effluent samples from painted or fired-in nAg filter disks. Results indicated that in general, greater than 90% of the eluted silver was due to Ag+ dissolution rather than nAg release. Additionally, a filter disk prepared with fired-in nAg exhibited a lower % released in the nanoparticle form (nAg = 5% of total Ag in effluent) compared to painted on nAg (nAg = 14% of total Ag in effluent). The findings of this study suggest that chlorinated influent water has minimal impact on silver elution from ceramic filters under simulated natural water conditions, and thus, the recommendation to avoid the use of chlorinated water with ceramic filters is not necessary under most conditions.

Interaction of calcium, phosphorus and natural organic matter in electrochemical recovery of phosphate

To address the issues of eutrophication and the potential risk of phosphorus (P) shortage, it is essential to remove and recover P from P-containing streams to close this nutrient cycle. Electrochemical induced calcium phosphate (CaP) precipitation was shown to be an efficient method for P recovery. However, the influence of natural organic matter (NOM) is not known for this treatment. In this paper, the behavior of NOM and its effect on CaP precipitation was studied. In contrast to studies where NOM hindered CaP precipitation, results show that the interaction of NOM with CaP improves the removal of P, independent of the types of NOM. The P removal at the average increased from 43.8 ± 4.9% to 58.5 ± 1.2% in the presence of 1.0 mg L−1 NOM. Based on the yellow color of the CaP product, NOM is co-precipitated. The bulk solution pH with and without buffers has totally different effects on the precipitation process. Without buffer, CaP precipitates on the cathode surface in a wide pH range (pH 4.0–10.0). However, the precipitation process is completely inhibited when the bulk solution is buffered at pH 4.0 and 6.0. This is probably due to neutralization of OH− by the buffers. Regardless of the presence or absence of NOM and solution pH, the recovered products are mainly amorphous CaP unless the electrolysis time was increased to seven days with 4.0 A m−2, in which crystalline CaP formed. These findings advance our understanding on the interaction of Ca, P and NOM species for the application of electrochemical method for P recovery from real wastewater.

Solar photoelectro-Fenton treatment of a mixture of parabens spiked into secondary treated wastewater effluent at low input current

Aqueous mixtures of methyl, ethyl and propyl paraben (MeP, EtP and PrP) prepared in real urban wastewater with low conductivity were treated by solar photoelectro-Fenton (SPEF) process at low input current (j=10mAcm−2) using a pre-pilot plant with an electrochemical reactor equipped with an air-diffusion cathode to electrogenerate H2O2 and a boron-doped diamond (BDD) or RuO2-based anode. Comparative trials in simulated water matrices with or without Cl− in the absence of natural organic matter (NOM) always led to a slower decay of parabens concentration and total organic carbon (TOC). This was mainly due to the superior regeneration of Fe2+ from photoreduction of Fe(III) complexes formed with NOM in real wastewater compared to that from Fe(OH)2+. In all matrices, a catalyst concentration as low as 0.20mM Fe2+ was enough to ensure the production of OH in the bulk from Fenton’s reaction. SPEF with BDD yielded a complete removal of parabens in 180min and 66% mineralization at 240min. This gave rise to the greatest mineralization current efficiencies reported so far, up to 1000%, with a low energy consumption of 84kWh (kg TOC)−1. The synergy between homogeneous and heterogeneous catalysis, which allowed the efficient dosage of OH and M(OH) at low j, with simultaneous action of high UV power from sunlight justified such a good performance. Analogous apparent rate constants were determined for MeP, EtP and PrP. Slower decays were found with RuO2-based anode due to its lower oxidation power. As a result, the MCE was 425% as maximum, but a lower energy consumption of 52kWh (kg TOC)−1 was needed. Since the role of active chlorine was of minor importance, the formation of toxic, refractory chloroderivatives was minimized. All by-products were transformed into malic, formic and oxalic acids prior to total mineralization.

Natural Organic Matter Concentration Impacts the Interaction of Functionalized Diamond Nanoparticles with Model and Actual Bacterial Membranes.

Changes to nanoparticle surface charge, colloidal stability, and hydrodynamic properties induced by interaction with natural organic matter (NOM) warrant consideration in assessing the potential for these materials to adversely impact organisms in the environment. Here, we show that acquisition of a coating, or "corona", of NOM alters the hydrodynamic and electrokinetic properties of diamond nanoparticles (DNPs) functionalized with the polycation poly(allylamine HCl) in a manner that depends on the NOM-to-DNP concentration ratio. The NOM-induced changes to DNP properties alter subsequent interactions with model biological membranes and the Gram-negative bacterium Shewanella oneidensis MR-1. Suwannee River NOM induces changes to DNP hydrodynamic diameter and apparent ζ-potential in a concentration-dependent manner. At low NOM-to-DNP ratios, DNPs aggregate to a limited extent but retain a positive ζ-potential apparently due to nonuniform adsorption of NOM molecules leading to attractive electrostatic interactions between oppositely charged regions on adjacent DNP surfaces. Diamond nanoparticles at low NOM-to-DNP ratios attach to model membranes to a larger extent than in the absence of NOM (including those incorporating lipopolysaccharide, a major bacterial outer membrane component) and induce a comparable degree of membrane damage and toxicity to S. oneidensis. At higher NOM-to-DNP ratios, DNP charge is reversed, and DNP aggregates remain stable in suspension. This charge reversal eliminates DNP attachment to model membranes containing the highest LPS contents studied due to electrostatic repulsion and abolishes membrane damage to S. oneidensis. Our results demonstrate that the effects of NOM coronas on nanoparticle properties and interactions with biological surfaces can depend on the relative amounts of NOM and nanoparticles.

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0–835ppm) or Suwanee River Fulvic Acid (SRFA) (0–955ppm). No evidence was found for reduction of uranyl by either form of NOM after 24h of exposure. The following three size fractions were considered in this study: (1) ≥0.2μm (Fh–NOM aggregates), (2) 0.02–0.2μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh–NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl–Fh–NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0–500ppm); at the highest NOM concentrations (500–955ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII–edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh–NOM aggregates. In the absence of NOM, uranyl formed dominantly inner–sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the proportion of uranyl–Fh inner-sphere sorption complexes decreased relative to uranyl–ESHA or uranyl–SRFA complexes, which comprised up to ∼60% of the total uranyl in the systems studied. At pH 7.0, uranyl–NOM complexes were also present in the Fh–NOM aggregates in the concentration ranges of ESHA or SRFA considered; however, the proportion of these complexes was smaller at pH 7.0 than at pH 4.6 and did not increase significantly with increasing NOM concentration.