Photodegradation of estrone enhanced by dissolved organic matter under simulated sunlight

In the present work the degradation of estrone (E1) a natural estrogenic hormone has been studied under simulated solar irradiation. The photodegradation of E1 has been investigated in the absence and in the presence of 7.7-8.9 mg L⁻¹ of dissolved organic carbon (DOC), under solar light simulation with irradiance approximating that of the sun. DOC extracts from different origins have been used. Half-lives ranging between 3.9 h and 7.9 h were observed. Results indicated that E1 was photodegraded even in the absence of DOC. The presence of DOC was found to enhance the degradation of E1. Experiments performed with the addition of reactive species scavengers (azide ions and 2-propanol) have shown that these two species play a significant role in the photodegradation. Some experiments have been performed with a DOC previously submitted to solar irradiation. Changes in optical and physico-chemical properties of DOC strongly affect its photoinductive properties, and hence its efficiency on E1 degradation. A part of the study consisted in the investigation of photoproducts structures. Five photoproducts were shown by chromatographic analysis: one arising from direct photolysis and the four others from DOC photoinduced degradation.     

UV-induced photochemical heterogeneity of dissolved and attached organic matter associated with cyanobacterial blooms in a eutrophic freshwater lake

Cyanobacterial blooms represent a significant ecological and human health problem worldwide. In aquatic environments, cyanobacterial blooms are actually surrounded by dissolved organic matter (DOM) and attached organic matter (AOM) that bind with algal cells. In this study, DOM and AOM fractionated from blooming cyanobacteria in a eutrophic freshwater lake (Lake Taihu, China) were irradiated with a polychromatic UV lamp, and the photochemical heterogeneity was investigated using fluorescence excitation–emission matrix (EEM)-parallel factor (PARAFAC) analysis and synchronous fluorescence (SF)-two dimensional correlation spectroscopy (2DCOS). It was shown that a 6-day UV irradiation caused more pronounced mineralization for DOM than AOM (59.7% vs. 41.9%). The EEM-PARAFAC analysis identified one tyrosine-, one humic-, and two tryptophan-like components in both DOM and AOM, and high component photodegradation rates were observed for DOM versus AOM (k > 0.554 vs. <0.519). Moreover, SF-2DCOS found that the photodegradation of organic matters followed the sequence of tyrosine-like > humic-like > tryptophan-like substances. Humic-like substances promoted the indirect photochemical reactions, and were responsible for the higher photochemical rate for DOM. The lower photodegradation of AOM benefited the integrality of cells in cyanobacterial blooms against the negative impact of UV irradiation. Therefore, the photochemical behavior of organic matter was related to the adaptation of enhanced-duration cyanobacterial blooms in aquatic environments.     

Development and application of functional assays for freshwater dissolved organic matter

A series of 11 standardised, reproducible, assays have been developed of physico-chemical functions of dissolved organic matter (DOM) in freshwaters. The assays provide quantitative information on light absorption, fluorescence, photochemical fading, pH buffering, copper binding, benzo(a)pyrene binding, hydrophilicity and adsorption to alumina. To obtain DOM for the assays, a 45 L sample of filtered freshwater was rotary-evaporated to reduce the volume to ca. 500 cm3. The concentrate was then passed through a strong cation exchanger, in the Na+ form, to remove alkaline-earth cations, and then through 0.7 and 0.2 microm filters. Eight samples, two each from a lake and three streamwaters, were processed. The yields of dissolved organic carbon (DOC) ranged from 70% to 107% (average 91%). The samples of DOM, stored in the dark at 4 degrees C, retained their functional assay characteristics for up to 7 months. When assaying the concentrates, parallel assays were performed with Suwannee River fulvic acid (SRFA), as a quality control standard. For most of the assays, the results for eight freshwater DOM samples are similar to those obtained with SRFA, the chief exception being the greater hydrophilicity of the DOM samples. For eight of the assays, variability among the DOM samples is significantly (p < 0.01) greater than can be explained by analytical error, i.e. by comparison with results for the SRFA quality standard; the three exceptional assays are photochemical fading, copper binding and benzo(a)pyrene binding. The two lakewater samples studied gave the most extreme assay results, probably because of the influence of phytoplankton-derived DOM. Significant correlations of hydrophilicity and adsorption with optical absorbance may mean that some DOM functional properties can be predicted from comparatively simple measurements.     

Estimation of the hydrophobic fraction of dissolved organic matter in water samples using UV photometry

In this study, we tested a simple and rapid method for the estimation of carbon in the hydrophobic fraction of dissolved organic matter (DOM) of different origin (spruce, pine, and beech litter) in soil water. The method is based on the fact that the hydrophobic fraction of DOM contains almost entirely the aromatic moieties of DOM. Thus, it showed a clearly distinct light absorption at 260 nm compared to the hydrophilic fraction. This light absorption was directly proportional to the concentration of the hydrophobic fraction. Moreover, it was independent of the concentration of the hydrophilic fraction. We compared the concentrations of hydrophobic DOM estimated by the UV method with those of the conventional fractionation using chromatographic columns of XAD-8 macroporous resin and found an excellent agreement between the two methods for both solutions from laboratory sorption experiments and field samples of forest floor leachates and subsoil porewaters. In addition, the absorption at 260 nm of hydrophobic DOM proved to be independent of pH values ranging from 2.0 to 6.5. Compared to the conventional chromatographic fractionation, the method using the UV absorption at 260 nm is less time consuming, needs a much smaller sample volume, and showed a better reproducibility. However, its use is restricted to water samples of low nitrate (<25 mg L⁻¹) and Fe (<5 mg L⁻¹) concentrations and, probably, with the hydrophobic fraction dominated by aromatic compounds deriving from degradation of lignin.     

Characteristics of dissolved organic matter following 20 years of peatland restoration

The changes in the amounts and composition of dissolved organic matter (DOM) following long-term peat restoration are unknown, although this fraction of soil organic matter affects many processes in such ecosystems. We addressed this lack of knowledge by investigating a peatland in south-west Germany that was partly rewetted 20 years ago. A successfully restored site and a moderately drained site were compared, where the mean groundwater levels were close to the soil surface and around 30 cm below surface, respectively. The concentrations of dissolved organic carbon (DOC) at 4 depths were measured over one year. The specific absorbance was measured at 280 nm and the fluorescence spectra were used to describe the aromaticity and complexity of DOM.The investigations showed that 20 years of peatland restoration was able to create typical peatland conditions. The rewetted site had significantly lower DOC concentrations at different depths compared to the drained site. The specific UV absorbance showed that the rewetted site had a lower level of aromatic DOM structures. The decreasing specific UV absorbance might indicate an increasing contribution of small organic molecules to DOM. It was hypothesized that the decreasing DOC concentrations and the relative enrichment of small, readily degradable organic molecules, reflect the slower decomposition of organic matter after the re-establishment of the water table. Seasonal trends provided substantial evidence for our hypothesis that reduced DOC concentrations were caused by reduced peat decomposition. During summer, the elevated DOC values were accompanied by an increase in DOM aromaticity and complexity. Our results demonstrated a close link between C mineralization and DOC production. We concluded that long-term peatland restoration in the form of the successful re-establishment of the water table might result in reduced peat decomposition and lower DOC concentrations. The restoration of peatlands seems to have a positive impact on C sequestration.     

Natural versus wastewater derived dissolved organic carbon: implications for the environmental fate of organic micropollutants

The interaction of organic micropollutants with dissolved organic carbon (DOC) can influence their transport, degradation and bioavailability. While this has been well established for natural organic carbon, very little is known regarding the influence of DOC on the fate of micropollutants during wastewater treatment and water recycling. Dissolved organic carbon-water partition coefficients (K_DOC) for wastewater derived and reference DOC were measured for a range of micropollutants using a depletion method with polydimethylsiloxane disks. For micropollutants with an octanol-water partition coefficient (log K_OW) greater than 4 there was a significant difference in K_DOC between reference and wastewater derived DOC, with partitioning to wastewater derived DOC over 1000 times lower for the most hydrophobic micropollutants. The interaction of nonylphenol with wastewater derived DOC from different stages of a wastewater and advanced water treatment train was studied, but little difference in K_DOC was observed. Organic carbon characterisation revealed that reference and wastewater derived DOC had very different properties due to their different origins. Consequently, the reduced sorption capacity of wastewater derived DOC may be related to their microbial origin which led to reduced aromaticity and lower molecular weight. This study suggests that for hydrophobic micropollutants (log K_OW > 4) a higher concentration of freely dissolved and thus bioavailable micropollutants is expected in the presence of wastewater derived DOC than predicted using K_DOC values quantified using reference DOC. The implication is that naturally derived DOC may not be an appropriate surrogate for wastewater derived DOC as a matrix for assessing the fate of micropollutants in engineered systems.     

Photosensitized degradation of amoxicillin in natural organic matter isolate solutions

Amoxicillin is a widely used antibiotic and has been detected in natural waters. Its environmental fate is in part determined by hydrolysis, and, direct and indirect photolysis. The hydrolysis rate in distilled water and water to which five different isolated of dissolved organic matter (DOM) was added, were evaluated. In the five different DOM solutions hydrolysis accounted for 5-18% loss of amoxicillin. Direct and indirect photolysis rates were determined using a solar simulator and it appeared that indirect photolysis was the dominant loss mechanism. Direct photolysis, in a solar simulator, accounted for 6-21% loss of amoxicillin in the simulated natural waters. The steady-state concentrations of singlet oxygen, ¹ΔO₂ (∼10⁻¹³ M) and hydroxyl radical, •OH (∼10⁻¹⁷ M) were obtained in aqueous solutions of five different dissolved organic matter samples using a solar simulator. The bimolecular reaction rate constant of ¹ΔO₂ with amoxicillin was measured in the different solutions, kΔO₂ = 1.44 × 10⁴ M⁻¹ s⁻¹. The sunlight mediated amoxicillin loss rate with ¹ΔO₂ (∼10⁻⁹ s⁻¹), and with •OH (∼10⁻⁷ s⁻¹), were also determined for the different samples of DOM. While ¹ΔO₂ only accounted for 0.03-0.08% of the total loss rate, the hydroxyl radical contributed 10-22%. It appears that the direct reaction of singlet and triplet excited state DOM (³DOM^∗) with amoxicillin accounts for 48-74% of the loss of amoxicillin. Furthermore, the pseudo first-order photodegradation rate showed a positive correlation with the sorption of amoxicillin to DOM, which further supported the assumption that excited state DOM^∗ plays a key role in the photochemical transformation of amoxicillin in natural waters. This is the first study to report the relative contribution of all five processes to the fate of amoxicillin in aqueous solution.     

A model for predicting dissolved organic carbon distribution in a reservoir water using fluorescence spectroscopy

A number of water treatment works (WTW) in the north of England (UK) have experienced problems in reducing the dissolved organic carbon (DOC) present in the water to a sufficiently low level. The problems are experienced in autumn/winter when the colour increases and the coagulant dose at the WTW needs to be increased in order to achieve sufficient colour removal. However, the DOC content of the water varies little throughout the year. To investigate this further, the water was fractionated using resin adsorption techniques into its hydrophobic (fulvic and humic acid fractions) and hydrophilic (acid and non-acid fractions) components. The fractionation process yields useful information on the changing concentration of each fraction but is time consuming and labour intensive. Here, a method of rapidly determining fraction concentration was developed using fluorescence spectroscopy. The model created used synchronous spectra of fractionated material compared against bulk water spectra and predicted the fraction concentrations to within 10% for a specific water. The model was unable to predict fraction concentrations for waters from a different watershed.     

Interactions of diuron with dissolved organic matter from organic amendments

Diuron is frequently detected in some drinking water reservoirs under the Burgundy vineyards, where organic amendments are applied. The environmental effect of these amendments on pesticide transport is ambiguous: on the one hand it could enhance their retention by increasing soil organic carbon content; on the other hand, dissolved organic matter (DOM) could facilitate their transport. Elutions were performed using columns packed with glass beads in order to investigate DOM-diuron interactions, and the possible co-transport of diuron and DOM. Four organic amendments (A, B, C and D) were tested; C and D were sampled at fresh (F) and mature (M) stages. An increase in diuron leaching was observed only for A and D_F amendments (up to 16% compared to the DOM-free blank samples), suggesting a DOM effect on diuron transport. These results could be explained by the higher DOM leaching for A and D_F compared to B, C_F, C_M and D_M increasing diuron-DOM interactions. These interactions seem to be related to the aromatic and aliphatic content of the DOM, determining formation of hydrogen and non-covalent bonds. The degree of organic matter maturity does not seem to have any effect with amendment C, while a reduction in diuron leaching is observed between D_F and D_M. After equilibrium dialysis measurement of diuron-DOM complexes, it appeared that less than 3% of the diuron applied corresponded to complexes with a molecular weight > 1000 Da. Complexes < 1000 Da could also take part in this facilitated transport.     

Nutrient and dissolved organic carbon removal from water using mining and metallurgical by-products

Excess nutrient input to water bodies frequently results in algal blooms and development of oxygen deficient conditions. Mining or metallurgical by-products can potentially be utilised as filtration media within water treatment systems such as constructed wetlands, permeable reactive barriers, or drain liners. These materials may offer a cost-effective solution for the removal of nutrients and dissolved organic carbon (DOC) from natural waters. This study investigated steel-making, alumina refining (red mud and red sand) and heavy mineral processing by-products, as well as the low-cost mineral-based material calcined magnesia, in laboratory column trials. Influent water and column effluents were analysed for pH and flow rate, alkalinity, nutrient species and DOC, and a range of major cations and anions. In general, by-products with high Ca or Mg, and to a lesser extent those with high Fe content, were well-suited to nutrient and DOC removal from water. Of the individual materials examined, the heavy mineral processing residue neutralised used acid (NUA) exhibited the highest sorption capacity for P, and removed the greatest proportions of all N species and DOC from influent water. In general, NUA and mixtures containing NUA, particularly those with calcined magnesia or red mud/red sand were the most effective in removing nutrients and DOC from influent water. Post-treatment effluents from columns containing NUA and NUA/steel-making by-product, NUA/red sand and NUA/calcined magnesia mixtures exhibited large reductions in DOC, P and N concentrations and exhibited a shift in nutrient ratios away from potential N- and Si-limitation and towards potential P-limitation. If employed as part of a large-scale water treatment scheme, use of these mining and metallurgical by-products for nutrient removal could result in reduced algal biomass and improved water quality. Identification and effective implementation of mining by-products or blends thereof in constructed wetlands or other intervention structures to augment nutrient and DOC retention has considerable potential as an aquatic ecosystem management tool.     

Ozone enhanced removal of natural organic matter from drinking water sources

The use of ozone as a pre-oxidant or intermediate oxidant in drinking-water treatment is becoming increasingly common. The ozonation of natural source waters containing natural organic matter produces biodegradable by-products such as organic acids, aldehydes, and ketoacids. These organic by-products serve as carbon source for bacteria, potentially causing regrowth problems in distribution systems. The measurement of biodegradable dissolved organic carbon (BDOC) provides quantitative insight into the amount of BDOC that is present. In drinking-water treatment, removal of BDOC can also reduce the formation potential of chlorination disinfection by-products such as trihalomethanes and haloacetic acids. Removal of BDOC was optimal at an applied ozone:DOC ratio of 2:1 (mg/mg) for source waters containing DOC levels ranging from 3 to 6 mg/liter. The use of biotreatment resulted in a 40–50% decrease in DOC, a 90–100% reduction in aldehydes, and a 40–60% reduction in trihalomethane formation potential. No removal of bromate ion and dibromoacetic acid was observed. A positive correlation was obtained between BDOC and assimilable organic carbon; both parameters indicate a tendency to plateau at an applied ozone/DOC weight ratio of 2:1.     

Relating freshwater organic matter fluorescence to organic carbon removal efficiency in drinking water treatment

Monthly raw and clarified water samples were obtained for 16 UK surface water treatment works. The fluorescence excitation-emission matrix (EEM) technique was used for the assessment of total organic carbon (TOC) removal and organic matter (OM) characterisation. The impact of algae presence in water on TOC removal, and its relationship with fluorescence, was analysed. Fluorescence peak C intensity was found to be a sensitive and reliable measure of OM content. Fluorescence peak C emission wavelength and peak T intensity (reflecting the degree of hydrophobicity and the microbial fraction, respectively) were found to characterize the OM; the impact of both on TOC removal efficiency was apparent. OM fluorescence properties were shown to predict TOC removal, and identify spatial and temporal variations. Previous work indicates that the trihalomethane (THM) concentration of treated water can be predicted from the raw water TOC concentration. The simplicity, sensitivity, speed of analysis and low cost, combined with potential for incorporation into on-line monitoring systems, mean that fluorescence spectroscopy offers a robust analytical technique to be used in conjunction with, or in place of, other approaches to OM characterisation and THM formation prediction.     

Characterization of dissolved organic matter in drinking water sources impacted by multiple tributaries

The characterization of dissolved organic matter (DOM) in drinking water sources is important as this material contributes to the formation of disinfection by-products (DBPs) and affects how water treatment unit operations are optimized. Drinking water utilities often draw water from sources impacted by multiple tributaries, with possible shifts in DOM concentrations and reactivity over time, depending on specific environmental conditions. In this study, results are presented on the characterization of DOM under varying ambient conditions from the four main tributaries of Lake Mead, a large reservoir in the southwest United States. The tributaries include the Las Vegas Wash (LVW), Muddy River (MR), Virgin River (VR) and the upper Colorado River (UCR). One additional sample was collected at the outflow of the reservoir (lower Colorado River (LCR)). The DOM was characterized by both bulk parameters (specific ultraviolet absorbance (SUVA)) and specific physicochemical properties, i.e. size, polarity and fluorescence. The analyses were performed emphasizing limited changes in its natural configuration by eliminating analytical preparation steps, excluding sample filtration (0.45 microm filter). Results indicate that each tributary had a different molecular weight distribution, as well as fluorescence properties, which helped in the identification of the relative source of DOM (allochthonous versus autochthonous). The largest apparent molecular weight distribution was observed for DOM samples collected at the MR site, which is fed mostly by groundwater seepage. The smallest apparent molecular weight was observed for DOM collected at the LCR site, suggesting that retention in the reservoir resulted in a decrease in molecular weight as a probable result of photo oxidation and microbial processes. Fluorescence analysis aided the differentiation of DOM by clearly identifying waters that were affected by microbial activity (LVW, UCR, and LCR), either by wastewater influence or by autochthonous processes, versus limited microbial influence (MR and VR). Polarity analysis revealed clear differences in the hydrophobic/hydrophilic nature between waters, including temporal differences within individual waters at a particular site. The DOM from the LVW and VR sites had higher hydrophobic character, as measured by retention onto non-polar sorbents. Additionally, the DOM collected at the LCR had the least hydrophobic character. This type of analysis would be beneficial to utilities who want to better understand and manage their source waters, especially in the evaluation of temporal variation within a watershed.     

Trends in hydrometeorological conditions and stream water organic carbon in boreal forested catchments

Temporal trends in stream water total organic carbon (TOC) concentration and export were studied in 8 forested headwater catchments situated in eastern Finland. The Seasonal Kendall test was conducted to identify the trends and a mixed model regression analysis was used to describe how catchment characteristics and hydrometeorological variables (e.g. precipitation, air and stream water temperatures, and atmospheric deposition) related to the variation in the concentration and export of stream water TOC. The 8 catchments varied in size from 29 to 494 ha and in the proportion of peatland they contained, from 8 to 70%. Runoff and TOC concentration were monitored for 15-29 years (1979-2006). Trends and variation in TOC levels were analysed from annual and seasonal time series. Mean annual TOC concentration increased significantly in seven of the eight catchments. The trends were the strongest in spring and most apparent during the last decade of the study period. The slopes of the trends were generally smaller than the variation in TOC concentration between years and seasons and between catchments. The annual TOC export showed no clear trends and values were largely determined by the temporal variability in runoff. Annual runoff showed a decreasing trend in two of the eight catchments. Mean annual air and stream water temperatures showed increasing trends, most clearly seen in the summer and autumn series. According to our modeling results, stream water temperature, precipitation and peatland percentage were the most important variables explaining annual and most seasonal TOC concentrations. The atmospheric deposition of SO₄, NH₄, and NO₃ decreased significantly over the study period, but no significant link with TOC concentration was found. Precipitation was the main hydrometeorological driver of the TOC export. We concluded that stream water TOC concentrations and exports are mainly driven by catchment characteristics and hydrometeorological factors rather than trends in atmospheric acid deposition.     

Atrazine removal from water by polycation-clay composites: Effect of dissolved organic matter and comparison to activated carbon

Atrazine removal from water by two polycations pre-adsorbed on montmorillonite was studied. Batch experiments demonstrated that the most suitable composite poly (4-vinylpyridine-co-styrene)-montmorillonite (PVP-co-S90%-mont.) removed 90-99% of atrazine (0.5-28 ppm) within 20-40 min at 0.367% w/w. Calculations employing Langmuir's equation could simulate and predict the kinetics and final extents of atrazine adsorption. Column filter experiments (columns 20 × 1.6 cm) which included 2 g of the PVP-co-S90%-mont. composite mixed with excess sand removed 93-96% of atrazine (800 ppb) for the first 800 pore volumes, whereas the same amount of granular activated carbon (GAC) removed 83-75%. In the presence of dissolved organic matter (DOM; 3.7 ppm) the efficiency of the GAC filter to remove atrazine decreased significantly (68-52% removal), whereas the corresponding efficiency of the PVP-co-S90%-mont. filter was only slightly influenced by DOM. At lower atrazine concentration (7 ppb) the PVP-co-S90%-mont. filter reduced even after 3000 pore volumes the emerging atrazine concentration below 3 ppb (USEPA standard). In the case of the GAC filter the emerging atrazine concentration was between 2.4 and 5.3 μg/L even for the first 100 pore volumes. Thus, the PVP-co-S90%-mont. composite is a new efficient material for the removal of atrazine from water.     

Continuous fluorescence excitation-emission matrix monitoring of river organic matter

Real-time fluorescence monitoring has been mostly performed in marine systems, with little progress being made in the application of fluorescence excitation-emission matrix (EEM) spectroscopy, especially for freshwater monitoring. This paper presents a two weeks experiment where real-time fluorescence EEM data have been obtained for Bourn Brook, Birmingham, UK, using an in-situ fibre-optic probe. Fluorescence EEMs were measured every 3 min for two weeks, with control ‘grab’ samples every hour analyzed for fluorescence EEMs as well as pH, conductivity and dissolved organic carbon. Comparison of real-time and control samples showed an excellent agreement, with no evidence of fibre-optic probe fouling. EEMs of different character were identified using self-organizing maps, which demonstrated seven clusters of fluorescence EEMs which related to the intensity of fluorescence and relative intensities of peak T₁ and T₂ vs. peak C and peak A fluorescence. Fluorescence intensity of peaks A and C were observed to increase with rainfall, and a diesel pollution event was detected through an increase in T₂ fluorescence.     

Modeling heavy metal uptake by sludge particulates in the presence of dissolved organic matter

The uptake of the seven heavy metal ions Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II) by sludge particulates in single-metal systems was investigated. Results showed that under acidic and neutral pH conditions, the uptake of all heavy metals by sludge particulates increases with the increase of pH. However, in the alkaline pH region, the uptake of Cu(II), Ni(II), and Co(II) decreases with the increase of pH, primarily due to the high dissolved organic matter (DOM) concentration in high pH conditions. Based on chemical reactions among heavy metal, sludge solids, and DOM, a mathematical model describing metal uptake as functions of DOM and pH was developed. The stability constants of metal–sludge and metal–DOM complexes can be determined using this model in conjunction with experimental metal uptake data. Results showed that, for the secondary sludge sample collected from Baltimore Back River Wastewater Treatment plant on March 1997, the stability constants of Cu(II)–sludge complex (log K_S) and Cu(II)–DOM complex (log K_L) are 5.3±0.2 and 4.7±0.3, respectively; for Ni(II), they are 4.0±0.2 and 3.9±0.2, respectively. Results also showed that under neutral and low pH conditions (pH<8), the DOM effects on metal uptake for all heavy metals are insignificant. Therefore, the DOM term in the model can be ignored. Results showed that, for the secondary sludge sample collected from Baltimore Back River Wastewater Treatment plant on December 1996, the estimated log K_S values of metal–sludge complexes for Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II) are, respectively, 3.6±0.2, 3.0±0.1, 5.5±0.1, 4.8±0.1, 3.1±0.1, 5.1±0.1, and 4.4±0.3.     

Fate of effluent organic matter and DBP precursors in an effluent-dominated river: A case study of wastewater impact on downstream water quality

The impact of treated wastewater discharges on downstream water quality was evaluated in an effluent-dominated stream in the Southwest USA. The fate and transport of effluent organic matter (EfOM) and disinfection by-product (DBP) precursors was studied. Nitrification and biodegradation were important mechanisms. Changes in DBP formation potential along the river appeared to correlate with dissolved organic carbon (DOC) and organic nitrogen concentrations and specific ultraviolet absorbance. The mean oxidation state of carbon (MOC) decreased in value along the river. MOC decreases paralleled decreases in the biodegradability of residual DOC (i.e., lower biodegradable DOC/DOC ratio). The EfOM was biodegradable by up to 40 percent, both in the stream and in a laboratory reactor, and many DBP precursors (e.g., haloacetonitriles, certain nitrosamines) decreased in concentration. Alternatively, the DBP yields for trihalomethanes or haloacetic acids either remained the same or increased slightly, suggesting that these precursors were part of the recalcitrant organic matter (OM).     

Thermal fluorescence quenching properties of dissolved organic matter

The fluorescence excitation-emission matrices of dissolved organic matter (DOM) are investigated between 10 and 45 degrees C for river and waste waters and organic matter standards. With increased temperature, fluorescence intensity is quenched. It is demonstrated that for a range of river and wastewater samples, that tryptophan-like fluorescence exhibits a greater range of quenching (between 20+/-4% and 35+/-5%) than fulvic-like fluorescence (19+/-4 to 26+/-3%) over this temperature range. Humic substance standards exhibit similar fulvic-like (23+/-4%) fluorescence thermal quenching properties to river water samples (23+/-3%); however none of the samples exhibit quenching of tryptophan-like fluorescence to the same extent as the tryptophan standards (approximately 50%). Thermal fluorescence quenching is related to the exposure of the fluorophores to the heat source; our findings suggest that the tryptophan-like groups within DOM is more exposed in untreated wastewaters than in treated wastewaters riverine DOM. Thermal fluorescence properties have the potential to be used to source DOM, to provide additional chemical structural information, to temperature correct laser-induced remotely sensed DOM fluorescence, and to characterise DOM through the wastewater treatment process.     

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.