The impact of climate change on the treatability of dissolved organic matter (DOM) in upland water supplies: A UK perspective

Climate change in the UK is expected to cause increases in temperatures, altered precipitation patterns and more frequent and extreme weather events. In this review we discuss climate effects on dissolved organic matter (DOM), how altered DOM and water physico-chemical properties will affect treatment processes and assess the utility of techniques used to remove DOM and monitor water quality. A critical analysis of the literature has been undertaken with a focus on catchment drivers of DOM character, removal of DOM via coagulation and the formation of disinfectant by-products (DBPs). We suggest that: (1) upland catchments recovering from acidification will continue to produce more DOM with a greater hydrophobic fraction as solubility controls decrease; (2) greater seasonality in DOM export is likely in future due to altered precipitation patterns; (3) changes in species diversity and water properties could encourage algal blooms; and (4) that land management and vegetative changes may have significant effects on DOM export and treatability but require further research. Increases in DBPs may occur where catchments have high influence from peatlands or where algal blooms become an issue. To increase resilience to variable DOM quantity and character we suggest that one or more of the following steps are undertaken at the treatment works: a) ‘enhanced coagulation’ optimised for DOM removal; b) switching from aluminium to ferric coagulants and/or incorporating coagulant aids; c) use of magnetic ion-exchange (MIEX) pre-coagulation; and d) activated carbon filtration post-coagulation. Fluorescence and UV absorbance techniques are highlighted as potential methods for low-cost, rapid on-line process optimisation to improve DOM removal and minimise DBPs.

Evaluation of optical techniques for characterising soil organic matter quality in agricultural soils

Soil organic matter (SOM) is one of the main global carbon pools. It is a measure of soil quality as its presence increases carbon sequestration and improves physical and chemical soil properties. The determination and characterisation of humic substances gives essential information of the maturity and stresses of soils as well as of their health. However, the determination of the exact nature and molecular structure of these substances has been proven difficult. Several complex techniques exist to characterise SOM and mineralisation and humification processes. One of the more widely accepted for its accuracy is nuclear magnetic resonance (NMR) spectroscopy. Despite its efficacy, NMR needs significant economic resources, equipment, material and time. Proxy measures like the fluorescence index (FI), cold and hot-water extractable carbon (CWC and HWC) and SUVA-254 have the potential to characterise SOM and, in combination, provide qualitative and quantitative data of SOM and its processes. Spanish and British agricultural cambisols were used to measure SOM quality and determine whether similarities were found between optical techniques and 1H NMR results in these two regions with contrasting climatic conditions. High correlations (p < 0.001) were found between the specific aromatic fraction measured with 1H NMR and SUVA-254 (Rs = 0.95) and HWC (Rs = 0.90), which could be described using a linear model. A high correlation between FI and the aromatics fraction measured with 1H NMR (Rs = −0.976) was also observed. In view of our results, optical measures have a potential, in combination, to predict the aromatic fraction of SOM without the need of expensive and time consuming techniques.

Modeling the photo-oxidation of dissolved organic matter by ultraviolet radiation in freshwater lakes: implications for mercury bioavailability

Uncertainties in projected ultraviolet (UV) radiation may lead to future increases in UV irradiation of freshwater lakes. Because dissolved organic carbon (DOC) is the main binding phase for mercury (Hg) in freshwater lakes, an increase in DOC photo-oxidation may affect Hg speciation and bioavailability. We quantified the effect of DOC concentration on the rate of abiotic DOC photo-oxidation for five lakes (DOC = 3.27–12.3 mg L−1) in Kejimkujik National Park, Canada. Samples were irradiated with UV-A or UV-B radiation over a 72-h period. UV-B radiation was found to be 2.36 times more efficient at photo-oxidizing DOC than UV-A, with energy-normalized rates of dissolved inorganic carbon (DIC) production ranging from 3.8 × 10−5 to 1.1 × 10−4 mg L−1 J−1 for UV-A, and from 6.0 × 10−5 to 3.1 × 10−4 mg L−1 J−1 for UV-B. Energy normalized rates of DIC production were positively correlated with DOC concentrations. Diffuse integrated attenuation coefficients were quantified in situ (UV-A Kd = 0.056–0.180 J cm−1; UV-B Kd = 0.015–0.165 J cm−1) and a quantitative depth-integrated model for yearly DIC photo-production in each lake was developed. The model predicts that, UV-A produces between 3.2 and 100 times more DIC (1521–2851 mg m−2 year−1) than UV-B radiation (29.17–746.7 mg m−2 year−1). Future increases in UV radiation may increase DIC production and increase Hg bioavailability in low DOC lakes to a greater extent than in high DOC lakes.

The development of soil organic matter in restored biodiverse Jarrah forests of South-Western Australia as determined by ASE and GCMS

Background, aim and scope Soil organic matter (SOM) is known to increase with time as landscapes recover after a major disturbance; however, little is known about the evolution of the chemistry of SOM in reconstructed ecosystems. In this study, we assessed the development of SOM chemistry in a chronosequence (space for time substitution) of restored Jarrah forest sites in Western Australia. Materials and methods Replicated samples were taken at the surface of the mineral soil as well as deeper in the profile at sites of 1, 3, 6, 9, 12, and 17 years of age. A molecular approach was developed to distinguish and quantify numerous individual compounds in SOM. This used accelerated solvent extraction in conjunction with gas chromatography mass spectrometry. A novel multivariate statistical approach was used to assess changes in accelerated solvent extraction (ASE)-gas chromatography-mass spectrometry (GCMS) spectra. This enabled us to track SOM developmental trajectories with restoration time. Results Results showed total carbon concentrations approached that of native forests soils by 17 years of restoration. Using the relate protocol in PRIMER, we demonstrated an overall linear relationship with site age at both depths, indicating that changes in SOM chemistry were occurring. Conclusions The surface soils were seen to approach native molecular compositions while the deeper soil retained a more stable chemical signature, suggesting litter from the developing diverse plant community has altered SOM near the surface. Our new approach for assessing SOM development, combining ASE-GCMS with illuminating multivariate statistical analysis, holds great promise to more fully develop ASE for the characterisation of SOM.

Characterization of organic matter in sediment cores of the Todos os Santos Bay, Bahia, Brazil, by elemental analysis and (13)C NMR

The impact of human activity on the sediments of Todos os Santos Bay in Brazil was evaluated by elemental analysis and (13)C Nuclear Magnetic Resonance ((13)C NMR). This article reports a study of six sediment cores collected at different depths and regions of Todos os Santos Bay. The elemental profiles of cores collected on the eastern side of Frades Island suggest an abrupt change in the sedimentation regime. Auto-regressive Integrated Moving Average (ARIMA) analysis corroborates this result. The range of depths of the cores corresponds to about 50 years ago, coinciding with the implantation of major onshore industrial projects in the region. Principal Component Analysis of the (13)C NMR spectra clearly differentiates sediment samples closer to the Subae estuary, which have high contents of terrestrial organic matter, from those closer to a local oil refinery. The results presented in this article illustrate several important aspects of environmental impact of human activity on this bay. (C) 2011 Elsevier Ltd. All rights reserved.

The use of polyacrylamides (PAMs) for removing natural organic matter (NOM) from Paraiba do Sul River (Brazil)

This work assesses the efficiency of polyacrylamides for natural organic matter (NOM) removal from Paraiba do Sul River (Brazil) raw water for drinking purposes. Jar tests were performed following an experimental design protocol. Three kinds of polyacrylamides (anionic, cationic, and non-ionic) at 0.2 mg L(-1) were tested. After coagulation, turbidity, DOC, UVA(254) and SCAN (UV-absorbing material) were determined. Color and pH were also measured. It was found that polyacrylamides did not reduce the amounts of alum and lime needed in the process and that the amount of alum alone for removing UV-absorbing organic matter is significantly higher. Efficiency of the coagulation process decreased as follows: non-ionic -> cationic -> anionic -> no polyacrylamide. Removal efficiencies for the best case were: 100%, 90%, 83%, and 68% for turbidity, DOC, UVA(254), and SCAN, respectively.

Characterization of organic matter from composting of different residues by physicochemical and spectroscopic methods

Chemical and spectroscopic methods were used to characterize organic matter transformations during the composting process. Four different residue mixtures were studied: P1 - garden trimmings (GT) only, P2 - GT plus fresh cattle manure, P3 - GT plus orange pomace and P4 - GT plus filter cake. The thermophilic phase was not reached in PI compost, but the P2, P3 and P4 composts showed all three typical process phases. The thermophilic phase and CEC/C ratio stabilized after 90 days, while C/N ratio and the ash content stabilized after 60 days. The increasing E(4)/E(6) ratio indicated oxidation reactions occurring during the process in the material from P2, P3 and P4. The (13)C NMR and FTIR results suggested extraction of both pectin and lignin in the HA-like fraction. The CEC/C ratio, temperature and E(4)/E(6) ratio showed that within 90 days P2, P3 and P4 composts were humified. However, material from P1 did not show characteristics of humified compost. From these data, it is apparent that C/N ratio and ash content are not reliable methods for monitoring the composting process. (C) 2009 Elsevier Ltd. All rights reserved.

Application of chemometric methods in the evaluation of chemical and spectroscopic data on organic matter from Oxisols in sewage sludge applications

Chemometric methods can contribute to soil research by permitting the extraction of more information from the data. The aim of this work was to use Principal Component Analysis to evaluate data obtained through chemical and spectroscopic methods on the changes in the humification process of soil organic matter from two tropical soils after sewage sludge application. In this case, humic acids extracted from Typic Eutrorthox and Typic Haplorthox soils with and without sewage sludge application for 7 consecutive years were studied. The results obtained for all of the samples and methods showed two clusters: samples extracted from the two soil types. These expected results indicated the textural difference between the two soils was more significant than the differences between treatments (control and sewage sludge application) or between depths. In this case, an individual chemometric treatment was made for each type of soil. It was noted that the characterization of the humic acids extracted from soils with and without sewage sludge application after 7 consecutive years using several methods supplies important results about changes in the humification degree of soil organic matter, These important result obtained by Principal Component Analysis justify further research using these methods to characterize the changes in the humic acids extracted from sewage sludge-amended soils. (C) 2009 Elsevier B.V. All rights reserved.

Characterization by Fluorescence of Organic Matter from Oxisols under Sewage Sludge Applications

Sewage sludge from wastewater treatment contains organic matter and plant nutrients that can play an important role in agricultural production and the maintenance of soil fertility, The present study has aimed to evaluate the degree of humification following sewage sludge application of soil organic matter by laser-induced fluorescence and humic acids using ultraviolet-visible fluorescence, and including comparison with Fourier-transform infrared spectroscopy and elemental analysis. Sewage sludge applications to the soil caused a decrease in the degree of humification of the soil organic matter and humic acids for both a Typic Eutrorthox (clayey) soil and a Typic Haplorthox (sandy) soil of around 14 and 27%, respectively. This effect is probably clue to incorporation of newly formed humic substances from the sewage sludge into the characteristics of less humified material, and to the indigenous soil humic substances. The minor alterations observed in the clay soil probably occurred due to both the greater mineral association, which better stabilized the indigenous soil organic matter, and the higher microbial activity in this soil, which accelerated sewage sludge mineralization. Sewage sludge applications increased the C content for the clay and sandy soils by 7.4 and 15.4 g kg(-1), respectively, suggesting a positive effect on these two soils.

Facilitated heterogeneous photodegradation of dissolved organic matter by particulate iron

The photochemical degradation of dissolved organic matter (DOM) derived from the leaves of River Red Gum (Eucalyptus camaldulensis) was examined, with a particular focus on the photochemical generation of CO₂, consumption of O₂, and the effect of particulate iron minerals on these photochemical reactions. Solutions of leaf leachate were irradiated with ultraviolet and visible light in the presence and absence of amorphous iron oxides. Addition of fresh iron oxide was found to increase the rate of photodegradation of the organic matter by up to an order of magnitude compared to the reactions without added iron oxide. The ratio of CO₂ produced to O₂ consumed was ~1:1 in both the presence and absence of iron oxyhydroxide. The reactivity of the iron oxides was dependent on the preparation method and decreased with increased storage time. These results suggest that photochemical reactions on particle surfaces should be considered when examining carbon transformation in aquatic ecosystems, especially at sites with potential for the production of iron oxyhydroxides.

Photodegradation, interaction with iron oxides and bioavailability of dissolved organic matter from forested floodplain sources

Photochemical degradation of dissolved organic matter (DOM) can influence food webs by altering the availability of carbon to microbial communities, and may be particularly important following periods of high DOM input (e.g. flooding of forested floodplains). Iron oxides can facilitate these reactions, but their influence on subsequent organic products is poorly understood. Degradation experiments with billabong (= oxbow lake) water and river red gum (Eucalyptus camaldulensis) leaf leachate were conducted to assess the importance of these reactions in floodplain systems. Photochemical degradation of DOM in sunlight-irradiated quartz tubes (with and without amorphous iron oxide) was studied using gas chromatography and UV-visible spectroscopy. Photochemical reactions generated gaseous products and small organic acids. Bioavailability of billabong DOM increased following irradiation, whereas that of leaf leachate was not significantly altered. Fluorescence excitation-emission spectra suggested that the humic component of billabong organic matter was particularly susceptible to degradation, and the source of DOM influenced the changes observed. The addition of amorphous iron oxide increased rates of photochemical degradation of leachate and billabong DOM. The importance of photochemical reactions to aquatic systems will depend on the source of the DOM and its starting bioavailability, whereas inputs of freshly formed iron oxides will accelerate the processes.

Changes in organic-matter dynamics and physicochemistry, associated with riparian vegetation loss and river regulation in floodplain wetlands of the Murray River, Australia

Extensive clearing of floodplain forests potentially reduces organic matter available to floodplain wetlands. Furthermore, on rivers regulated to provide irrigation water in summer, floodplain wetlands that were previously inundated in spring, now flood in summer/autumn. In the Murray–Darling Basin, Australia, this has changed the timing of organic matter entering the aquatic phase, since leaf fall peaks in summer. Field surveys and mesocosm experiments on floodplain wetlands on the River Murray revealed faster processing rates of leaves in summer/autumn than spring, and no difference between cleared and forested wetlands. Temperature and leaf carbon : nitrogen ratio could not explain these differences, and instead, changes to leaf chemistry associated with ‘terrestrial ageing’ between peak leaf fall in summer and inundation in spring is more likely. The results indicated that the reduction of input of organic matter through riparian tree clearing and changing the timing of inundation interact to alter organic-matter standing stocks and rates of decomposition in floodplain wetlands. Restoring both natural timing of high flows and riparian vegetation might be required for recovery of these wetlands.

Removal of natural organic matter though membrane filtration and subsequent effect on disinfectant decay

This study aims to evaluate the effectiveness of membrane filtration in removing natural organic matters (NOMs) from four different source waters and the subsequent effect that it has on total chlorine (TC) demand of these waters. Source water samples were filtered sequentially through membranes with molecular weight cut-off of 3,500, 1,000 and 200 Da as well as RO membrane. The source waters and sequentially filtered samples were dosed with chlorine and the residual chlorine data were used to estimate the TC demand of these waters. A robust chlorine decay model constructed in AQUASIM software was used to do so. More than 80% of the chlorine demand in untreated surface water sources was found to be contributed mainly by NOMs that were larger than 3,500 Da. However, for water treated by granular filtration, the chlorine demand was found to be contributed by NOMs which were down to 200 Da. Sequential filtration through all four membranes reduced chlorine demand by more than 94% in surface waters and 84% in waters treated by granular filtration. Significant reduction in the formation of trihalomethane can be achieved if water is treated by appropriate membranes after granular media filtration. © 2014 © 2014 Balaban Desalination Publications. All rights reserved.