Fluorescence spectroscopic characterization of dissolved organic matter fractions in soils in soil aquifer treatment

This work investigated the effect of soil aquifer treatment (SAT) operation on the fluorescence characteristics of dissolved organic matter (DOM) fractions in soils through laboratory-scale soil columns with a 2-year operation. The resin adsorption technique (with XAD-8 and XAD-4 resins) was employed to characterize the dissolved organic matter in soils into five fractions, i.e., hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N), and hydrophilic fraction (HPI). The synchronous fluorescence spectra revealed the presence of soluble microbial byproduct- and humic acid-like components and polycyclic aromatic compounds in DOM in soils, and SAT operation resulted in the enrichment of these fluorescent materials in all DOM fractions in the surface soil (0–12.5 cm). More importantly, the quantitative method of fluorescence regional integration was used in the analysis of excitation–emission matrix (EEM) spectra of DOM fractions in soils. The cumulative EEM volume (Φ _{T, n} ) results showed that SAT operation led to the enrichment of more fluorescent components in HPO-A and TPI-A, as well as the dominance of less fluorescent components in HPO-N, TPI-N, and HPI in the bottom soil (75–150 cm). Total Φ _{T, n} values, which were calculated as $ {\Phi_{{T,n}}} \times {\mathrm{DOC}} $ , suggested an accumulation of fluorescent organic matter in the upper 75 cm of soil as a consequence of SAT operation. The distribution of volumetric fluorescence among five regions (i.e., P _{i, n} ) results revealed that SAT caused the increased content of humic-like fluorophores as well as the decreased content of protein-like fluorophores in both HPO-A and TPI-A in soils.     

The development of a chemical 'fingerprint' to characterise dissolved organic matter in natural waters

A suite of twelve assays has been used to 'fingerprint' dissolved organic matter (DOM). The assays were applied directly to filtered natural water samples. Temperature, pH and conductivity accounted for the environmental conditions on-site. Bulk carbon characteristics were assayed by measuring UV absorbance at 200 and 240 nm, colour in grade Hazen, DOC (dissolved organic carbon), fluorescence (excitation 370 nm, emission 450 nm) and the complexation of phenol itself. Measuring hydroxybenzenes ('monophenolics'), polyhydroxybenzenes ('polyphenolics') and total phenolics with the Gibbs, Prussian Blue and Folin-Ciocalteau assays, respectively, determined the phenolics pool. The methodology was tested on six freshwater sites in North Wales chosen to provide differences in vegetation, land-use and water chemistry and sampled once during each season. A novel approach for the presentation of the data has been developed that combines all range normalised assay results for each site and each season within one polar plot, hence the term 'fingerprint'. The data was also analysed using principal component factor analysis. Assays characterised as determining the chemical properties of DOM contributed to Factor 1 and explained 59% of the variation in the data. Assays apparently determined by the water matrix, contributed to Factor 2 and explained 20% of the variation within the data. The factor scores obtained for each site showed more variation for assays relating to the chemical properties of DOM than to the surrounding water matrix. The methodology was found to detect chemical changes within DOM for each site throughout the year and different responses for different sites.     

Comparison of dissolved organic matter fractions in a secondary effluent and a natural water

This research compared the structural and chemical characteristics among dissolved organic matter (DOM) fractions within the same source and among different origins. Samples taken from the Taiping Wastewater Treatment Plant (TWTP) (Harbin, China) and from the Songhuajing River (SR), Heilongjiang Province, China were chosen to represent waters containing DOM of wastewater origin and of natural-water origin, respectively. DOM was fractionated using XAD resins into five fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). The SR fractions were more UV-sensitive and more reactive with chlorine in formation of trihalomethanes (THMs) than the TWTP secondary effluent (TSE) fractions. The aromatic character peaks in the Fourier-transform infrared (FT-IR) spectra of SR fractions were clearer than those of TSE fractions. On the other hand, the peaks of carbohydrates in TSE fractions were more prominent in comparison with SR fractions. In addition, the amide-2 peak was present in the spectra of all the five TSE fractions but not visible in the spectra of SR fractions. The fluorescence results showed that SR DOM fractions contained more fulvic acid-like fluorescent compounds while TSE DOM fractions had higher amounts of protein-like fluorescent components.     

Lead forms in urban turfgrass and forest soils as related to organic matter content and pH

Identification of reference streams and human disturbance gradients are crucial steps in assessing the effects of human disturbances on stream health. We describe a process for identifying reference stream reaches and assessing disturbance gradients using readily available, geo-referenced stream and human disturbance databases. We demonstrate the utility of this process by applying it to wadeable streams in Michigan, USA, and use it to identify which human disturbances have the greatest impact on streams. Approximately 38% of cold-water and 16% of warm-water streams in Michigan were identified as being in least-disturbed condition. Conversely, approximately 3% of cold-water and 4% of warm-water streams were moderately to severely disturbed by landscape human disturbances. Anthropogenic disturbances that had the greatest impact on moderately to severely disturbed streams were nutrient loading and percent urban land use within network watersheds. Our process for assessing stream health represents a significant advantage over other routinely used methods. It uses inter-confluence stream reaches as an assessment unit, permits the evaluation of stream health across large regions, and yields an overall disturbance index that is a weighted sum of multiple disturbance factors. The robustness of our approach is linked to the scale of disturbances that affect a stream; it will be less robust for identifying less degraded or reference streams with localized human disturbances. With improved availability of high-resolution disturbance datasets, this approach will provide a more complete picture of reference stream reaches and factors contributing to degradation of stream health.     

Monitoring of eutrophication by microbial uptake kinetics of dissolved organic matter in waters

The monitoring of eutrophication can be performed by measuring the turnover times of amino acids in watermasses using the Wright-Hobbie uptake kinetics approach.The substrate specificity of amino acids varies greater with turnover times than with sampling location in watermasses with a certain water type. Thus a specific substrate among the essential amino acids should be selected to use for measuring the turnover time, in order to monitor precisely the state of trophic excitation within the steady-state oscillation in a certain aquatic system. On the other hand, either singular or plural substrates among the essential amino acids can be used for measuring the turnover time for the identification of a watermass, relevant to eutrophication.     

High-frequency measurements reveal spatial and temporal patterns of dissolved organic matter in an urban water conveyance

Stormwater runoff in urban areas can contribute high concentrations of dissolved organic matter (DOM) to receiving waters, potentially causing impairment to the aquatic ecosystem of urban streams and downstream water bodies. Compositional changes in DOM due to storm events in forested, agricultural, and urban landscapes have been well studied, but in situ sensors have not been widely applied to monitor stormwater contributions in urbanized areas, leaving the spatial and temporal characteristics of DOM within these systems poorly understood. We deployed fluorescent DOM (FDOM) sensors at upstream and downstream locations within a study reach to characterize the spatial and temporal changes in DOM quantity and sources within an urban water conveyance that receives stormwater runoff. Baseflow FDOM decreased over the summer season as seasonal flows upstream transported less DOM. FDOM fluctuated diurnally, the amplitude of which also declined as the summer season progressed. During storms, FDOM concentrations were rapidly elevated to values orders of magnitude greater than baseflow measurements, with greater concentrations at the downstream monitoring site, revealing high contributions from stormwater outfalls between the two locations. Observations from custom, in situ fluorometers resembled results obtained using laboratory methods for identifying DOM source material and indicated that DOM transitioned to a more microbially derived composition as the summer season progressed, while stormwater contributions contributed DOM from terrestrial sources. Deployment of a mobile sensing platform during varying flow conditions captured spatial changes in DOM concentration and composition and revealed contributions of DOM from outfalls during stormflows that would have otherwise been unobserved.     

Characterization of soil organic matter content of two sample size populations along a climatic transect

Soil organic matter (SOM) content was determined in two populations of soil samples that were taken from 0–2 soil depth. One population represented soil samples that were takenfrom a square of 25 cm² in size (small-S population) and the other population represented soil samples that were taken from a square of 2500 cm² in size (large-L population). Thesamples were collected on hillslopes in different climatic regions: Mediterranean (GIV), semi-arid (MAL), mildly-arid (MIS) and arid (KAL). The results of both S and L populationsshowed decreasing SOM mean and variance from the Mediterranean site to the arid site. Statistical and spatial characteristics of each population were compared between the climatic regions. In addition, comparison between the two populations was made foreach site. The difference in sample size did not significantly affect the mean values of SOM of the two populations in sitesGIV, MAL and KAL, but did affect the mean at site MIS. At all study sites, except for site MAL, the variance increased with decreasing sample size. At sites GIV and KAL the coefficient ofvariation of S population was higher (more than 1.5 times) thanthat of L population, whereas at sites MAL and MIS, the differences were negligible. The relationships between the valuesof S and L samples at the individual sampling points defined thebackground of the study sites, which reflects the effect of vegetation (type), grazing, biological crust and soil properties.It was found that at the extreme sites GIV and KAL the backgroundwas characterized by relatively low SOM content with small areas of high organic matter content. At site MIS the background wascharacterized by relatively high SOM with small areas of low organic matter content. At site MAL the background was not dominated by high values of SOM nor by low ones. The spatial pattern of L population became more simple with increasing aridity. At the relatively wet sites the spatial pattern did notdepend on the sample size while in the more arid sites it was sample size dependent. It was indicated that the spatial structure of SOM at the semi-arid and mildly arid sites is anisotropic whereas at the Mediterranean and arid sites it is isotropic.     

The occurrence of heavy metals in irrigated and non-irrigated arable soils,NW Albania

The study analysed the content of heavy metals in surface soil and sediment samples from the Bregu i Matit Plain in NW Albania in relation to irrigation in order to evaluate the soil pollution and the potential risk to human health. Evaluation of soil pollution was performed using the enrichment factor and geo-accumulation index. Contents of cadmium, chromium and nickel of irrigated soils were significantly higher than those of non-irrigated soil, while contents of lead (in three of the irrigated locations), zinc and arsenic (in one of the irrigated locations) were significantly lower. Correlation analysis (CA) and principal component analysis (PCA) indicated that the primary source of the first three metals was irrigation, and the last three metals were originated from other anthropic sources, like the use of chemicals, etc. Enrichment factor (E _f) calculation showed that irrigated soils were most enriched in cadmium, chromium, copper and nickel. Index of geo-accumulation (I _geo) revealed that arable soils of Bregu i Matit are unpolluted to moderately polluted with cadmium, chromium, copper and zinc and moderately to strongly polluted with nickel and arsenic. The presence of heavy metals in the studied soils indicates a potential risk of transfer of these elements in the food chain. Therefore, further studies on the speciation of heavy metals in the studied soils in order to evaluate their mobility are needed.     

Chironomid mouthpart deformities as indicator of environmental quality: a case study in Lake Trasimeno (Italy)

The aim of the present study was to monitor mouthpart deformities of Chironomus plumosus (Insecta-Diptera) in Lake Trasimeno (2000-2010) in relation with sediment contamination by heavy metals, which is one of the main causes of deformity induction. In Lake Trasimeno, concentrations of heavy metals in the investigated littoral zone were low, in comparison with those of the central area. By contrast, the incidence of deformities was much higher in the littoral station (2006-2009) than in the central area. In the littoral zone, the deformities progressively decreased and by 2010 reached values similar to those observed in the central area (2000-2002, 2010). This decrease was mainly due to the reduction of severe deformities, thus indicating an environmental quality recovery of this littoral sector. Chemical analysis revealed that the higher incidence of deformities in the littoral zone was not caused by heavy metal contamination, unless they may have contributed to a joint action with other toxicants. The present study on Lake Trasimeno provided additional evidence that chironomid mouthpart deformities can be used in biomonitoring programs to evaluate sediment contamination by toxicants. Since mouthpart deformities may also be induced by compounds not included in routine chemical analyses, they may better reflect sediment quality than chemical analysis alone.     

Size and resin fractionations of dissolved organic matter and trihalomethane precursors from four typical source waters in China

Dissolved organic matter (DOM) and its potential to form disinfection by-products (DBPs) during drinking water treatment raise challenges to water quality control. Understanding both chemical and physical characteristics of DOM in source waters is key to better water treatment. In this study, the DOM from four typical source waters in China was fractionated by XAD resin adsorption (RA) and ultrafiltration (UF) techniques. The trihalomethane formation potential (THMFP) of all fractions in the DOM were investigated to reveal the major THM precursors. The fraction distributions of DOM could be related to their geographical origins in a certain extent. The dominant chemical fraction as THM precursors in the DOM from south waters (East-Lake reservoir in Shenzhen and Peal rivers in Guangzhou) was hydrophobic acid (HoA). The size fraction with molecular weight (MW) <1 kDa in both south waters had the highest THMFP. The results of cluster analysis showed that the parameters of fractions including DOC percentage (DOC%), UV₂₅₄%, SUVA₂₅₄ (specific UV₂₅₄ absorbance) and THMFP were better for representing the differences of DOM from the studied waters than specific THMFP (STHMFP). The weak correlation between SUVA₂₅₄ and STHMFP for either size or XAD fractions suggests that whether SUVA₂₅₄ can be used as an indicator for the reactivity of THM formation is highly dependent on the nature of organic matter.     

Mobilization and plant accumulation of prometryne in soil by two different sources of organic matter

Prometryne is a selective herbicide of the s-triazine chemical family. Due to its weak absorption onto soil, it readily leaches down through the soil and contaminates underground water. Application of organic manure to soil has become a widespread practice as a disposal strategy to improve soil properties. In this study, we demonstrated the effect of pig manure compost (PMC) and lake-bed sludge (SL) on the sorption/desorption, mobility and bioavailability of prometryne in soil using comprehensive analysis approaches. Downward movement of prometryne was monitored in the packed soil column. Addition of PMC or SL decreased considerably the mobility and total concentration of prometryne in the soil leachate. Bioavailability analyses with wheat plants revealed that addition of the organic matter reduced accumulation of prometryne in tissues and increased plant elongation and biomass. These results indicate that the organic amendments are effective in modifying adsorption and mobility of the pesticide in soil.     

Changes in labile soil organic matter fractions following land use change from monocropping to poplar-based agroforestry systems in a semiarid region of Northeast China

Labile fractions of soil organic matter (SOM) respond rapidly to land management practices and can be used as a sensitive indicator of changes in SOM. However, there is little information about the effect of agroforestry practices on labile SOM fractions in semiarid regions of China. In order to test the effects of land use change from monocropping to agroforestry systems on labile SOM fractions, we investigated soil microbial biomass C (MBC) and N, particulate organic matter C (POMC) and N (POMN), as well as total organic C (TOC) and total N (TN) in the 0- to 15-cm and the 15- to 30-cm layers in 4-year-old poplar-based agroforestry systems and adjoining monocropping systems with two different soil textures (sandy loam and sandy clay loam) in a semiarid region of Northeast China. Our results showed that poplar-based agroforestry practices affected soil MBC, POMC, and POMN, albeit there was no significant difference in TOC and TN. Agroforestry practices increased MBC, POMC, and POMN in sandy clay loam soils. However, in sandy loam soils, agroforestry practices only increased MBC and even decreased POMC and POMN at the 0- to 15-cm layer. Our results suggest that labile SOM fractions respond sensitively to poplar-based agroforestry practices and can provide early information about the changes in SOM in semiarid regions of Northeast China and highlight that the effects of agroforestry practices on labile SOM fractions vary with soil texture.     

大气总悬浮颗粒中有机碳的测定

本文提出一种新的高灵敏度测定总悬浮颗粒中有机碳的方法一元素分析法。该方法是在氧化炉最佳温度为６００℃时,一步测定出样品中有机碳的含量,并成功地对齐齐哈尔市大气总悬浮颗粒中的有机碳进行了连续的监测。结果表明,总悬浮颗粒中有机碳的含量有较明显的变化规律。     

Classification of alluvial soils according to their potential environmental risk: a case study for Belgian catchments

Alluvial soils may represent important sinks of contaminants as a result of the deposition of contaminated sediments along the river by overbank flooding or after dredging. Because of the erosion of alluvial deposits or the release of contaminants from sediments, alluvial soils can also be a source of contamination. In this paper, a risk assessment for contaminated (alluvial) soils is presented. The approach, mainly based on physico-chemical soil characteristics, single extractions and leaching tests, is illustrated by means of a case study from four Belgian catchments. The extractions and leaching tests that were used have been validated by European testing programs and can provide valuable information for classifying the potential environmental risks of soils. Irrespective of the location, pH, organic carbon content and 'mobilisable' metal concentrations were the most important factors explaining 'mobile' metal concentrations in the alluvial soils. Additionally, the data of the physico-chemical soil characterization, extractions and leaching tests were combined with local and regional factors to classify the alluvial soils in different categories according to their actual and potential risk for the environment.