Effect of selected metal ions on the photocatalytic degradation of bog lake water natural organic matter

Herein we report the photocatalytic degradation of natural organic matter from a bog lake (Lake Hohloh, Black Forest, Germany) in the presence of 0, 5, and 10 μmol L⁻¹ of added Cu²⁺, Mn²⁺, Zn²⁺ and Fe³⁺. The reactions were followed by size exclusion chromatography with organic carbon detection (SEC-DOC) and by measurements of low molecular weight organic acids. Addition of Cu²⁺ had the largest effect of all four studied metals, leading to a retardation in the molecular size changes in NOM: degradation of the larger molecular weight fraction was inhibited leading to reduced production of smaller molecular weight metabolites. Similarly, addition of Cu²⁺ reduced the production of formic and oxalic acids, and reduced the bioavailability of the partially degraded NOM.     

Copper addition by organic matter degradation in the freshwater reaches of a turbid estuary

This study reports on the relationship between copper (Cu) behavior and organic matter (OM) transformation along the turbidity gradient in the freshwater reaches of the Gironde Estuary. During a one-year survey, surface water and suspended particulate matter (SPM) were sampled at least monthly at three sites along the Garonne Branch, representing the main fluvial branch of the Gironde Estuary. Additionally, a longitudinal high resolution profile was sampled along the Garonne Branch, covering the turbidity gradient from the river water endmember to the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of Cu in both the dissolved phases (< 0.2 μm, Cu_0.2 and < 0.02 μm, Cu_0.02) and particulate Cu (Cu_P) clearly suggested Cu_0.2 addition during summer, that increased the Cu_0.2 concentrations by a factor ~ 2, mainly manifested by an increase in the Cu_0.02 fraction. At the annual timescale (2004), this internal Cu reactivity increased Cu_0.02 fluxes in the Garonne Branch by ~ 20% (3.6 t year⁻¹), with the equivalent of ~ 2.9 t year⁻¹ derived from the Cu_P fraction and ~ 0.7 t year⁻¹ from the colloidal (0.02-0.2 μm) fraction, without involving and/or affecting the Cu_C18 (hydrophobic metal-organic complexes) fraction.Combining data on Cu speciation with the results obtained by several independent techniques (DOC and POC measurements, 3D-fluorescence, and TEM) suggested close relationships between Cu behavior and OM transformation/restructuration along the turbidity gradient in the Garonne Branch. The observed Cu_0.02 addition was related to increasing humification (humification index HIX increased from 9 to 12, network formation) and labile OM degradation (Iγ/Iα ratio decreased from 0.70 to 0.44), going along with decreasing DOC and POC concentrations. Mass-balances suggest that in the studied system, degradation of OM may account for the release of ~ 25 μmol potentially bioaccessible Cu_0.02 per mole of particulate organic carbon mineralized.     

Effects of copper, pH and hardness on the critical swimming performance of rainbow trout (Salmo gairdneri Richardson)

Critical swimming velocities of Salmo gairdneri at 12°C were determined in different combinations of copper; pH and hardness. Measurements were made after exposure for 0.5, 5, 10, and 30 days. When copper was not applied, hardness, pH and exposure time had no appreciable effect on critical performance. Copper had the greatest effect on swimming performance at 5 days of exposure. At pH 7.5–8.0, recovery from the initial depression was complete after 10 days of exposure, but critical swimming performance did not return to control levels in pH 6.0 treatments. For any given hardness, copper had a greater effect on critical speed at low than at high pH. A given copper treatment had a more pronounced effect at low than at high hardness.No distinction could be made among total, soluble, or extractable copper but predicted concentrations of 6 specific cupric ions varied with pH and hardness. Of these copper species, only Cu²⁺ and CuOH⁺ were found to be related significantly to critical performance.Oxygen consumption of trout was determined in different combinations of copper and pH. In the presence of copper the maximum oxygen consumption decreased and the energy expenditure for a given swimming speed increased.The above observations are discussed in relation to reported toxic actions of copper.     

Catalysis of copper corrosion products on chlorine decay and HAA formation in simulated distribution systems

This study investigated the effect of copper corrosion products, including Cu(II), Cu₂O, CuO and Cu₂(OH)₂CO₃, on chlorine degradation, HAA formation, and HAA speciation under controlled experimental conditions. Chlorine decay and HAA formation were significantly enhanced in the presence of copper with the extent of copper catalysis being affected by the solution pH and the concentration of copper corrosion products. Accelerated chlorine decay and increased HAA formation were observed at pH 8.6 in the presence of 1.0 mg/L Cu(II) compared with that observed at pH 6.6 and pH 7.6. Further investigation of chlorine decay in the presence of both Suwannee River NOM and Cu(II) indicated that an increased reactivity of NOM with dissolved and/or solid surface-associated Cu(II), rather than chlorine auto-decomposition, was a primary reason for the observed rapid chlorine decay. Copper corrosion solids [Cu₂O, CuO, Cu₂(OH)₂CO₃] exhibited catalytic effects on both chlorine decay and HAA formation. Contrary to the results observed when in the absence of copper corrosion products, DCAA formation was consistently predominant over other HAA species in the presence of copper corrosion products, especially at neutral and high pH. This study improves the understanding for water utilities and households regarding chlorine residuals and HAA concentrations in distribution systems, in particular once the water reaches domestic plumbing where copper is widely used.     

The chemistry of heavy metals in digested sewage sludge—II. Heavy metal complexation with soluble organic matter

Characterisitcs of copper-binding, in the soluble fraction of a digested sewage sludge, were determined using ion-selective electrodes. Results showed that ion exchange with protons is a principal component in copper binding and that the soluble organic matter has a cation exchange capacity of 8.86 m-equiv g⁻¹ at pH 6.5. A pH-dependent exchange constant, defined in terms of mole fractions of exchange components, describes the data in the pH range 2–8 and is independent of both pH and the extent of exchange in the range 5.5–8. Supplementary data include acid/base titration curves and simple kinetic measurements. Anion uptake is insignificant in the pH range 2.5–7. A model of the aqueous phase of a sewage sludge, containing soluble organic matter with only copper and protons as competing ions, predicts that at pH 7 over 99% of the copper present will be bound to the soluble organic matter.     

The chemistry of heavy metals in digested sewage sludge—I. Copper(II) complexation with soluble organic matter

Characterisitcs of copper-binding, in the soluble fraction of a digested sewage sludge, were determined using ion-selective electrodes. Results showed that ion exchange with protons is a principal component in copper binding and that the soluble organic matter has a cation exchange capacity of 8.86 m-equiv g⁻¹ at pH 6.5. A pH-dependent exchange constant, defined in terms of mole fractions of exchange components, describes the data in the pH range 2–8 and is independent of both pH and the extent of exchange in the range 5.5–8. Supplementary data include acid/base titration curves and simple kinetic measurements. Anion uptake is insignificant in the pH range 2.5–7. A model of the aqueous phase of a sewage sludge, containing soluble organic matter with only copper and protons as competing ions, predicts that at pH 7 over 99% of the copper present will be bound to the soluble organic matter.     

Aggregation and disaggregation of iron oxide nanoparticles: Influence of particle concentration, pH and natural organic matter

The surface coating, aggregation behavior and aggregate structure of unpurified iron oxide nanoparticles (NPs) at variable pH and in the absence and presence of natural organic matter (NOM, Suwannee River humic acid, SRHA) have been previously studied in Baalousha et al. [Baalousha, M., Manciulea, A., Cumberland, S., Kendall, K., Lead, J.R., Aggregation and surface properties of iron oxide nanoparticles; influence of pH and natural organic matter. Environ Toxicol Chem 2008; 27: 1875-1882.]. Here the aggregation behavior of iron oxide NPs at variable concentrations of NPs and SRHA, and the disaggregation behavior of iron oxide NP aggregates in the absence and presence of SRHA are investigated. The increase of NP concentration enhances their aggregation, particularly at pH values close to the point of zero charge (PZC). High concentration of SRHA (100 mg l^− 1) shifts the NP (100 mg l^− 1) PZC charge and aggregation maximum towards lower pHs, while low concentration (10 mg l^− 1) shows low or no effect. The disaggregation behavior of iron oxide NP aggregates was investigated at pH 7 and at increasing concentrations of SRHA. High concentrations (50 and 100 mg l^− 1) of SRHA induced the disaggregation of iron oxide NP aggregates with time, which was not the case at lower concentrations (10 mg l^− 1) or in the absence of SRHA. The disaggregation was triggered by the enhanced surface charge induced by the sorption of SRHA molecules. The disaggregation rate increased with SRHA concentration and decreased with time. Two regimes of disaggregation were identified, a fast regime of “fragmentation” at the first 15 days of the experiment and a slow regime of “erosion” afterwards. The formation of small aggregates of about 170 nm and surface coating of several nanometers of SRHA on iron oxide NPs confirm the role of NOM in the disaggregation process and indicate that NPs might mimic the behavior of natural colloids.     

Energy recovery in wastewater decontamination: Simultaneous photocatalytic oxidation of an organic substrate and electricity generation

The contemporary removal of organic pollutants from aqueous solution and electricity generation is studied in the present work by means of an experimental device resulting from the combination of a photocatalytic reactor and an electrochemical cell. The proposed system relies on the capability of Cu²⁺ ions to reduce in the presence of TiO₂, (solar) UV radiations and a sacrificial organic agent. In the anodic solution of the combined photoreactor-cell, Cu⁰ is oxidized to Cu²⁺ and the latter is reduced again to the lowest oxidation state. The use of different sacrificial agents ranging from formic acid (FA) to glycerol (GLY) to glucose (GLU) is investigated along with the adoption of two different cathodes for the cell, the first based again on the couple Cu²⁺/Cu⁰ and the second on the couple O₂/H₂O.     

Influences of pH, heavy metals and phosphate and their co-influences on the sorption of pentachlorophenol on cyanobacterial biomass

Influences of pH, two types of ions of transition metals (Cu²⁺, Cd²⁺), Na₃PO₄ and their co-influences on the sorption of pentachlorophenol (PCP) on cyanobacterial biomass derived from natural bloom were studied. Sorption of PCP significantly decreases with pH in the range of 3.25-9.00. Although sorption coefficient of ionized PCP is 8.51 times lower than that of neutral species, it is the dominant species at environmentally relevant pH and contributes more to the total sorption of PCP. In the presence of low concentration of Cu²⁺ (≤40 μmol L⁻¹), sorption of PCP was much lower than that of the blank. However, it increased gradually with Cu²⁺, and overpassed the blank when concentration of Cu²⁺ was higher than 50 μmol L⁻¹. Compared with the sole influence of pH, coexisted Cu²⁺ inhibited the sorption of PCP at pH of 3.25 and 4.35, but enhanced it in the pH range of 5.00-9.00. In the presence of Cd²⁺, sorption of PCP first increased then decreased rapidly and finally increased slightly again with Cd²⁺. Except for at pH of 9.00, sorption of PCP at other pH in the presence of Cd²⁺ was much lower than that solely affected by pH. In the presence of Na₃PO₄, sorption of PCP increased rapidly then maintained with Na₃PO₄. Under the influence of both Na₃PO₄ and pH, sorption of PCP at pH from 3.25 to 5.00 was lower than that solely affected by pH, while it increased with pH in the range of 5.00-9.00 and was higher than that solely affected by pH in the range of 6.00-9.00. Ion pairs of pentachlorophenolate-metal facilitated the sorption of PCP, which was largely dependent on pH illustrated by UV-visible and FTIR spectra. Speciations of metals and PCP and the stability constants of ion pairs of pentachlorophenolate-metal greatly affected the sorption. Ionic strength also played an important role for the sorption of PCP.     

Fatty acid fouling of reverse osmosis membranes: implications for wastewater reclamation

Effluent organic matter (EfOM) contributes significantly to organic fouling of reverse osmosis (RO) membranes in advanced wastewater reclamation. In this study, the effect of feed solution chemistry (solution pH and Ca²⁺ concentration) on the fouling of RO membranes by octanoic acid—selected to represent fatty acids in EfOM—is investigated. Crossflow fouling experiments demonstrate that RO membrane fouling is much more significant at solution pH below the pK_a of the octanoic acid (pK_a = 4.9) than at an elevated pH. Octanoic acid permeates across the membranes more readily at solution pH below its pK_a than at elevated pH. At pH below the octanoic acid pK_a, fouling behavior is not affected by calcium ions, whereas at elevated pH, the rate of flux decline decreases with higher calcium ion concentration. The effect of calcium on the fouling behavior was further verified from foulant-foulant adhesion forces, determined by atomic force microscopy (AFM) force measurements under solution chemistries identical to those of the crossflow fouling experiments. To investigate the implications of octanoic acid fouling for wastewater reclamation, the effect of octanoic acid on membrane fouling by a combination of organic foulants in the presence of calcium ions is studied. At a solution chemistry simulating that of typical wastewater effluents, the addition of octanoic acid to a feed solution containing alginate, bovine serum albumin, and Suwannee River natural organic matter, does not enhance membrane fouling behavior. This observation could be attributed to the significant contribution of the alginate-calcium complexes within the fouling layer to the total membrane resistance.     

Ultrafiltration of natural organic matter and black carbon: Factors influencing aggregation and membrane fouling

There are concerns about black carbon (BC), due to its potential for sorption of toxic pollutants and inevitably entering drinking water sources. This study aimed to evaluate factors affecting BC aggregation and membrane fouling in the ultrafiltration of river water. Hydrophilic carbon black (CB) was selected as a surrogate of submicron BC in natural waters. Calcium, pH, and natural organic matter (NOM) were found to influence CB aggregation. Calcium induced interparticle interactions in a pH range of 4.3-7.7. In river water at 0.3 mM Ca²⁺, CB remained as fine aggregates (<300 nm) that caused substantial filtration resistance. At 1.3 mM Ca²⁺, CB size increased to 2.2-3.3 μm and membrane fouling was reduced. Interactions between particles and NOM enhanced organic rejection and eliminated irreversible membrane fouling. BC in water resources is a noxious substance, but it was easily aggregated in hard waters and could enhance NOM removal in the ultrafiltration process.     

The effect of natural water conditions on the anti-bacterial performance and stability of silver nanoparticles capped with different polymers

This study evaluated the effect of natural water composition onto the bactericidal and physicochemical properties of silver nanoparticles (AgNPs) stabilized with three different polymeric compounds.All the nanoparticles behaved similarly in the water conditions tested. Compared to solutions with low organic matter content and monovalent ions, lower disinfection performances of AgNPs suspensions were obtained in the following order seawater ≤ high organic matter content water ≤ high divalent cations content synthetic water. Suspension of AgNPs in seawater and water with divalent cations (Ca²⁺ and Mg²⁺) formed larger AgNPs aggregates (less than 1400 nm) compared to other solutions tested (up to approximately 38 nm). The critical coagulation concentration (CCC) of AgNPs was determined to quantitatively evaluate the stability of the nanoparticle suspension in different water conditions. When the concentration of dissolved organic matter was increased from 0 mg/L to 5 mg/L, the CCC increased by a factor in the range of 2.19 ± 0.25 for all AgNPs in divalent solutions, but a smaller increase occurred, in the range of 1.54 ± 0.21 fold, when monovalent solutions were used.The concentration of ionic silver released indicated that the dissolved Ag⁺ (3.6-48.2 ppb) was less than 0.5% of the total mass of Ag⁰ added. At all the conditions tested, the concentration of silver ions in solution had a negligible contribution to the overall anti-bacterial performance of AgNPs.This study demonstrated that the anti-bacterial performance of AgNPs at selected natural water conditions decreases in the presence of dissolved natural organic matter or divalent ions, such as humic acid and calcium carbonate. These results may be helpful in understanding the toxicity of AgNP in various natural water conditions and in explaining the risk associated with discharging AgNP in natural aquatic systems.     

Ozone oxidation for the alleviation of membrane fouling by natural organic matter: A review

Membrane fouling by natural organic matter is one of the main problems that slow down the application of membrane technology in water treatment. O₃ is able to efficiently change the physico-chemical characteristics of natural organic matter in order to reduce membrane fouling. This paper presents the state-of-the-art knowledge of the reaction mechanisms between natural organic matter and molecular O₃ or OH radicals, together with an in-depth discussion of the interactions between natural organic matter and membranes that govern membrane fouling, inclusive the effect of O₃ oxidation on it.     

The toxicity of some forms of copper to rainbow trout

The lethal toxicity of copper to rainbow trout in hard water was found to be related to the total concentration at which soluble copper. Cu²⁻ and CuCO₃, was present in the water, rather than to the concentration of either of these two forms alone. It is suggested that, except in the presence of highly toxic organo-copper compounds, from a knowledge of the cupric ion concn, the pH, and the alkalinity of a water, the total concentration of soluble copper can be calculated and hence the toxicity of that water determined.     

Effects of inorganic complexing on the toxicity of copper to Daphnia magna

Effects of carbonate-bicarbonate, orthophosphate, and pyrophosphate on the toxicity of copper (II) to Daphnia magna were studied at constant pH and total hardness. Mortality rates and reciprocal survival times were directly correlated with cupric (Cu²⁺) and copper hydroxy (Cu(OH)n) ion activities as determined by equilibrium calculations. Toxicity was negatively related to activities of soluble copper carbonate (CuCO₃) and other complexes, and was found to be independent of dissolved copper or total copper concentrations.     

Formation of methyl iodide on a natural manganese oxide

This paper demonstrates that manganese oxides can initiate the formation of methyl iodide, a volatile compound that participates to the input of iodine into the atmosphere. The formation of methyl iodide was investigated using a natural manganese oxide in batch experiments for different conditions and concentrations of iodide, natural organic matter (NOM) and manganese oxide. Methyl iodide was formed at concentrations ≤1 μg L⁻¹ for initial iodide concentrations ranging from 0.8 to 38.0 mg L⁻¹. The production of methyl iodide increased with increasing initial concentrations of iodide ion and Mn sand and when pH decreased from 7 to 5. The hydrophilic NOM isolate exhibited the lowest yield of methyl iodide whereas hydrophobic NOM isolates such as Suwannee River HPOA fraction produced the highest concentration of methyl iodide. The formation of methyl iodide could take place through the oxidation of NOM on manganese dioxide in the presence of iodide. However, the implication of elemental iodine cannot be excluded at acidic pH. Manganese oxides can then participate with ferric oxides to the formation of methyl iodide in soils and sediments. The formation of methyl iodide is unlikely in technical systems such as drinking water treatment i.e. for ppt levels of iodide and low contact times with manganese oxides.     

Elemental and organic carbon in aerosols over urbanized coastal region (southern Baltic Sea, Gdynia)

Studies on PM 10, total particulate matter (TSP), elemental carbon (EC) and organic carbon (OC) concentrations were carried out in the Polish coastal zone of the Baltic Sea, in urbanized Gdynia. The interaction between the land, the air and the sea was clearly observed. The highest concentrations of PM 10, TSP and both carbon fractions were noted in the air masses moving from southern and western Poland and Europe. The EC was generally of primary origin and its contribution to TSP and PM 10 mass was on average 2.3% and 3.7% respectively. Under low wind speed conditions local sources (traffic and industry) influenced increases in elemental carbon and PM 10 concentrations in Gdynia. Elemental carbon demonstrated a pronounced weekly cycle, yielding minimum values at the weekend and maximum values on Thursdays. The role of harbors and ship yards in creating high EC concentrations was clearly observed. Concentration of organic carbon was ten times higher than that of elemental carbon, and the average OC contribution to PM 10 mass was very high (31.6%). An inverse situation was observed when air masses were transported from over the Atlantic Ocean, the North Sea and the Baltic Sea. These clean air masses were characterized by the lowest concentrations of all analysed compounds.Obtained results for organic and elemental carbon fluxes showed that atmospheric aerosols can be treated, along with water run-off, as a carbon source for the coastal waters of the Baltic Sea. The enrichment of surface water was more effective in the case of organic carbon (0.27 ± 0.19 mmol m⁻² d⁻¹). Elemental carbon fluxes were one order of magnitude smaller, on average 0.03 ± 0.04 mmol m⁻² d⁻¹. We suggest that in some situations atmospheric carbon input can explain up to 18% of total carbon fluxes into the Baltic coastal waters.     

Toxicity of 2,4-dinitrotoluene to terrestrial plants in natural soils

The presence of energetic materials (used as explosives and propellants) at contaminated sites is a growing international issue, particularly with respect to military base closures and demilitarization policies. Improved understanding of the ecotoxicological effects of these materials is needed in order to accurately assess the potential exposure risks and impacts on the environment and its ecosystems. We studied the toxicity of the nitroaromatic energetic material 2,4-dinitrotoluene (2,4-DNT) on alfalfa (Medicago sativa L.), barnyard grass (Echinochloa crusgalli L. Beauv.), and perennial ryegrass (Lolium perenne L.) using four natural soils varying in properties (organic matter, clay content, and pH) that were hypothesized to affect chemical bioavailability and toxicity. Amended soils were subjected to natural light conditions, and wetting and drying cycles in a greenhouse for 13 weeks prior to toxicity testing to approximate field exposure conditions in terms of bioavailability, transformation, and degradation of 2,4-DNT. Definitive toxicity tests were performed according to standard protocols. The median effective concentration (EC₅₀) values for shoot dry mass ranged from 8 to 229 mg kg^− 1, depending on the plant species and soil type. Data indicated that 2,4-DNT was most toxic in the Sassafras (SSL) and Teller (TSL) sandy loam soils, with EC₅₀ values for shoot dry mass ranging between 8 to 44 mg kg^− 1, and least toxic in the Webster clay loam soil, with EC₅₀ values for shoot dry mass ranging between 40 to 229 mg kg^− 1. The toxicity of 2,4-DNT for each of the plant species was significantly (p ≤ 0.05) and inversely correlated with the soil organic matter content. Toxicity benchmark values determined in the present studies for 2,4-DNT weathered-and-aged in SSL or TSL soils will contribute to development of an Ecological Soil Screening Level for terrestrial plants that can be used for ecological risk assessment at contaminated sites.     

Modeling copper partitioning in surface waters

Suspended particulate matter from the surface waters of the Susquehanna, Christina and Brandywine Rivers was collected by tangential flow filtration to study copper partitioning. Copper adsorption increased with an increase of suspended particles and decreased with low pH values or with an increase of dissolved organic matter. Effects of particulate organic matter on copper distribution between suspended particulate and solution phases were studied using modified aluminum oxide. An increase of particulate organic matter enhanced copper adsorption. Copper adsorption per mass of particulate organic carbon was similar for the different sources of suspended particles. A model, based on copper adsorption on particles and complexation with dissolved organic matter, was developed to assess copper partition coefficient as a function of the easily measurable water quality parameters: pH, alkalinity, dissolved organic carbon and particulate organic matter. The partitioning model was calibrated on pH edge data using suspended particles collected from the three rivers. The model was verified using partitioning data as a function of dissolved organic matter. The model adequately describes the system containing natural suspended solids collected from the surface waters.     

Influence of organic matter on the transport of Cryptosporidium parvum oocysts in a ferric oxyhydroxide-coated quartz sand saturated porous medium

To assess the effect of organic matter on the transport of Cryptosporidium parvum oocysts in a geochemically heterogeneous saturated porous medium, we measured the breakthrough and collision efficiencies of oocysts as a function of dissolved organic matter concentration in a flow-through column containing ferric oxyhydroxide-coated sand. We characterized the surface properties of the oocysts and ferric oxyhydroxide-coated sand using microelectrophoresis and streaming potential, respectively, and the amount of organic matter adsorbed on the ferric oxyhydroxide-coated sand as a function of the concentration of dissolved organic matter (a fulvic acid isolated from Florida Everglades water). The dissolved organic matter had no significant effect on the zeta potential of the oocysts. Low concentrations of dissolved organic matter were responsible for reversing the charge of the ferric oxyhydroxide-coated sand surface from positive to negative. The charge reversal and accumulation of negative charge on the ferric oxyhydroxide-coated sand led to increases in oocyst breakthrough and decreases in oocyst collision efficiency with increasing dissolved organic matter concentration. The increase in dissolved organic matter concentration from 0 to 20 mg L⁻¹ resulted in a two-fold decrease in the collision efficiency.