Magdalena Bieroza

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.

Nitrate in United Kingdom Rivers: Policy and Its Outcomes Since 1970

Modern conventional farming provides Western Europe and North America with reliable, high quality, and relatively cheap supplies of food and fiber, increasingly viewed as a potential source of fuel. One of the costs is continued widespread pollution of rivers and groundwater-predominantly by nutrients. In 1970, in both the United States and UK, farming was focused on maximizing yield and management practices were rapidly modernizing. Little attention was paid to the external impacts of farming. In 2010, diffuse pollution from agriculture is being seriously addressed by both voluntary and statutory means in an attempt to balance environmental costs with the continued benefits of agricultural production. In this paper we consider long-term changes in the concentration and flux of nitrate in five rural UK rivers to demonstrate the impact of agricultural intensification and subsequent policies to reduce diffuse pollution on river water quality between 1970 and 2010.

Understanding nutrient biogeochemistry in agricultural catchments: the challenge of appropriate monitoring frequencies.

We evaluate different frequencies of riverine nutrient concentration measurement to interpret diffuse pollution in agricultural catchments. We focus on three nutrient fractions, nitrate-nitrogen (NO3-N), total reactive phosphorus (TRP) and total phosphorus (TP) observed using conventional remote laboratory-based, low-frequency sampling and automated, in situ high-frequency monitoring. We demonstrate the value of low-frequency routine nutrient monitoring in providing long-term data on changes in surface water and groundwater nutrient concentrations. By contrast, automated high-frequency nutrient observations provide insight into the fine temporal structure of nutrient dynamics in response to a full spectrum of flow dynamics. We found good agreement between concurrent in situ and laboratory-based determinations for nitrate-nitrogen (Pearsons R = 0.93, p < 0.01). For phosphorus fractions: TP (R = 0.84, p < 0.01) and TRP (R = 0.79, p < 0.01) the relationships were poorer due to the underestimation of P fractions observed in situ and storage-related changes of grab samples. A detailed comparison between concurrent nutrient data obtained by the hourly in situ automated monitoring and weekly-to-fortnightly grab sampling reveals a significant information loss at the extreme range of nutrient concentration for low-frequency sampling.

Characterisation of dissolved organic matter fluorescence properties by PARAFAC analysis and thermal quenching

The fluorescence intensity of dissolved organic matter (DOM) in aqueous samples is known to be highly influenced by temperature. Although several studies have demonstrated the effect of thermal quenching on the fluorescence of DOM, no research has been undertaken to assess the effects of temperature by combining fluorescence excitation - emission matrices (EEM) and parallel factor analysis (PARAFAC) modelling. This study further extends previous research on thermal quenching by evaluating the impact of temperature on the fluorescence of DOM from a wide range of environmental samples, in the range 20 °C - 0 °C. Fluorescence intensity increased linearly with respect to temperature decrease at all temperatures down to 0 °C. Results showed that temperature affected the PARAFAC components associated with humic-like and tryptophan-like components of DOM differently, depending on the water type. The terrestrial humic-like components, C1 and C2 presented the highest thermal quenching in rural water samples and the lowest in urban water samples, while C3, the tryptophan-like component, and C4, a reprocessed humic-like component, showed opposite results. These results were attributed to the availability and abundance of the components or to the degree of exposure to the heat source. The variable thermal quenching of the humic-like components also indicated that although the PARAFAC model generated the same components across sites, the DOM composition of each component differed between them. This study has shown that thermal quenching can provide additional information on the characteristics and composition of DOM and highlighted the importance of correcting fluorescence data collected in situ.

Unravelling organic matter and nutrient biogeochemistry in groundwater-fed rivers under baseflow conditions: Uncertainty in in situ high-frequency analysis.

In agricultural catchments, diffuse nutrient fluxes (mainly nitrogen N and phosphorus P), are observed to pollute receiving waters and cause eutrophication. Organic matter (OM) is important in mediating biogeochemical processes in freshwaters. Time series of the variation in nutrient and OM loads give insights into flux processes and their impact on biogeochemistry but are costly to maintain and challenging to analyse for elements that are highly reactive in the environment. We evaluated the capacity of the automated monitoring to capture typically low baseflow concentrations of the reactive forms of nutrients and OM: total reactive phosphorus (TRP), nitrate nitrogen (NO3-N) and tryptophan-like fluorescence (TLF). We compared the performance of in situ monitoring (wet chemistry analyser, UV-vis and fluorescence sensors) and automated grab sampling without instantaneous analysis using autosamplers. We found that automatic grab sampling shows storage transformations for TRP and TLF and do not reproduce the diurnal concentration pattern captured by the in situ analysers. The in situ TRP and fluorescence analysers respond to temperature variation and the relationship is concentration-dependent. Accurate detection of low P concentrations is particularly challenging due to large errors associated with both the in situ and autosampler measurements. Aquatic systems can be very sensitive to even low concentrations of P typical of baseflow conditions. Understanding transformations and measurement variability in reactive forms of nutrients and OM associated with in situ analysis is of great importance for understanding in-stream biogeochemical functioning and establishing robust monitoring protocols.

Improving and testing geochemical speciation predictions of metal ions in natural waters

The ability of WHAM VII and NICA-Donnan models to predict free-ion activities of Cu in natural waters was examined from two perspectives, (i) the presence of EDTA and NTA contaminants, (ii) the need to improve estimates of HA and FA concentrations. Potentiometric responses of a Cu(II) ion-selective electrode were investigated in five assays containing dissolved organic matter (DOM) isolated from a series of polluted (urban) and relatively unpolluted (upland) streams in northern England. The [Cu]/[DOC] ratio in these assays spanned an environmentally realistic range of ∼1-500 μmol/g. Reasonably good agreement between measured and predicted Cu(2+) activities was obtained with both WHAM VII and NICA-Donnan models, assuming 65% of DOM as fulvic acid and including the measured EDTA and NTA concentrations, but generally the models overestimated the activities by a factor of ∼2. In contrast, the models over-predicted the Cu(2+) activities by up to 2 orders of magnitude at low [Cu]/[DOC] ratios in urban waters if anthropogenic ligands were not included in the model simulations. Three-dimensional fluorescence excitation-emission matrix (EEM) spectroscopy was used to measure the functional properties of the isolated DOM and to estimate the fractions of FA and HA present. Using these fractions in the models gave improvements in predictions compared to the 65% FA assumption, as shown by higher correlations, reduced error and reduced bias. These results highlight various issues with the use of the available speciation models for predicting free ion concentrations in natural waters, such as the use of the Biotic Ligand Model (BLM) for the derivation of environmental standards. It is clearly necessary to measure EDTA and NTA in waters with urban influences, while fluorescence measurements offer the possibility of appreciably improving the accuracy of predictions.

Assessment of Low pH Coagulation Performance Using Fluorescence Spectroscopy

Optimization of organic matter (OM) removal is of key importance for effective water treatment, as its presence affects treatment processes. In particular, OM increases the operational cost of treatment caused by increased coagulant and disinfectant demands. In the work reported here, fluorescence spectroscopy is used to assess the effect of changing coagulation pH on OM removal, character, and composition. The results of a 3-month trial of low pH coagulation operation at a major surface water treatment works in the Midlands region of the UK are discussed, together with the effect upon total organic carbon (TOC) removal. OM removal was assessed on the basis of both measured removal and fluorescence-inferred removal (through intensity-reduction measurements). Fluorescence spectroscopy demonstrated that optimized coagulation affects the quantitative and qualitative OM properties. Fluorescence analyses were shown to complement other OM measurements, with reductions of peak intensities correlating well with removal of TOC in a range of different treatment conditions.

The concentration-discharge slope as a tool for water quality management

Recent technological breakthroughs of optical sensors and analysers have enabled matching the water quality measurement interval to the time scales of stream flow changes and led to an improved understanding of spatially and temporally heterogeneous sources and delivery pathways for many solutes and particulates. This new ability to match the chemograph with the hydrograph has promoted renewed interest in the concentration-discharge (c-q) relationship and its value in characterizing catchment storage, time lags and legacy effects for both weathering products and anthropogenic pollutants. In this paper we evaluated the stream c-q relationships for a number of water quality determinands (phosphorus, suspended sediments, nitrogen) in intensively managed agricultural catchments based on both high-frequency (sub-hourly) and long-term low-frequency (fortnightly-monthly) routine monitoring data. We used resampled high-frequency data to test the uncertainty in water quality parameters (e.g. mean, 95th percentile and load) derived from low-frequency sub-datasets. We showed that the uncertainty in water quality parameters increases with reduced sampling frequency as a function of the c-q slope. We also showed that different sources and delivery pathways control c-q relationship for different solutes and particulates. Secondly, we evaluated the variation in c-q slopes derived from the long-term low-frequency data for different determinands and catchments and showed strong chemostatic behaviour for phosphorus and nitrogen due to saturation and agricultural legacy effects. The c-q slope analysis can provide an effective tool to evaluate the current monitoring networks and the effectiveness of water management interventions. This research highlights how improved understanding of solute and particulate dynamics obtained with optical sensors and analysers can be used to understand patterns in long-term water quality time series, reduce the uncertainty in the monitoring data and to manage eutrophication in agricultural catchments.