Relating dissolved organic matter fluorescence and functional properties

The fluorescence excitation–emission matrix properties of 25 dissolved organic matter samples from three rivers and one lake are analysed. All sites are sampled in duplicate, and the 25 samples include ten taken from the lake site, and nine from one of the rivers, to cover variations in dissolved organic matter composition due to season and river flow. Fluorescence properties are compared to the functional properties of the dissolved organic matter; the functional assays provide quantitative information on photochemical fading, buffering capacity, copper binding, benzo[a]pyrene binding, hydrophilicity and adsorption to alumina. Optical (absorbance and fluorescence) characterization of the dissolved organic matter samples demonstrates that (1) peak C (excitation 300–350 nm; emission 400–460 nm) fluorescence emission wavelength; (2) the ratio of peak T (excitation 220–235 nm; emission 330–370 nm) to peak C fluorescence intensity; and (3) the peak C fluorescence intensity: absorbance at 340 nm ratio have strong correlations with many of the functional assays. Strongest correlations are with benzo[a]pyrene binding, alumina adsorption, hydrophilicity and buffering capacity, and in many cases linear regression equations with a correlation coefficient >0.8 are obtained. These optical properties are independent of freshwater dissolved organic carbon concentration (for concentrations <10 mg L⁻¹) and therefore hold the potential for laboratory, field and on-line monitoring and prediction of organic matter functional properties.     

Fluorescence characterization of cross flow ultrafiltration derived freshwater colloidal and dissolved organic matter

3-D fluorescence excitation-emission matrix (EEM) spectrophotometry was applied to investigate the fluorescence characterization of colloidal organic matter (COM) and truly dissolved organic matter (DOM) from an urban lake and a rural river fractionated by the cross flow ultrafiltration (CFUF) process with a 1kDa membrane. Relatively high tryptophan-like fluorescence intensity is found in the urban water, although the fluorescence of both water samples is mainly dominated by humic/fulvic-like fluorophores. During CFUF processing, the fluorescence intensities of humic/fulvic-like materials in the retentate increased rapidly, but a slight increase is also observed in the permeate fluorescence intensity. Very different ultrafiltration behaviour occurred with respect to the tryptophan-like fluorophore, where both permeate and retentate fluorescence intensities increase substantially at the beginning of the CFUF process, then tend to remain constant at high concentration factor (cf) values. Comparison with tryptophan standards demonstrates that freshwater tryptophan-like fluorescence is not dissolved and 'free', but is, in part, colloidal and related to the ultrafiltration behaviour of fulvic/humic-like matter. A good linear relationship between the retentate humic/fulvic-like fluorescence intensity and organic carbon concentration further reveals that fluorescent humic/fulvic-like substances are the dominant contributors to colloidal organic carbon, mainly in the colloidal fraction.     

Effects of organic matter and ageing on the bioaccessibility of arsenic

Arsenic-contaminated soils may pose a risk to human health. Redevelopment of contaminated sites may involve amending soils with organic matter, which potentially increases arsenic bioaccessibility. The effects of ageing on arsenic-contaminated soils mixed with peat moss were evaluated in a simulated ageing period representing two years, during which arsenic bioaccessibility was periodically measured. Significant increases (p = 0.032) in bioaccessibility were observed for 15 of 31 samples tested, particularly in comparison with samples originally containing >30% bioaccessible arsenic in soils naturally rich in organic matter (>25%). Samples where percent arsenic bioaccessibility was unchanged with age were generally poor in organic matter (average 7.7%) and contained both arsenopyrite and pentavalent arsenic forms that remained unaffected by the organic matter amendments. Results suggest that the addition of organic matter may lead to increases in arsenic bioaccessibility, which warrants caution in the evaluation of risks associated with redevelopment of arsenic-contaminated land.     

Effect of pH and the role of organic matter in the adsorption of isoproturon on soils

Equilibrium measurements were carried out with the herbicide isoproturon on natural adsorbents (brown forest-, chernozem-, sandy soils and quartz) in different buffered media (pH 5, 7, 8 phosphate buffer). Adsorption isotherms were fitted by a multi-step adsorption equation providing numerical information used in the environmental propagation models and risk assessment works. In the adsorption of the slightly polar isoproturon the dissolved organic matter of the soil and the pH play an important role. At molecular level, results are interpreted by taking into consideration the hydrophobic interaction and the formation of hydrogen bonds between the surface and the solute. The observed adsorption behavior indicates that the organic matter content of the soils and its soluble fulvic acid, alkaline soluble humic acid and insoluble humin fractions were considerable different. The chernozem soil containing the highest amount of insoluble organic fraction proved to be a very efficient adsorbent. The brown forest and the sandy soils exhibit rather similar adsorbent properties but at pH 7 the latter containing more fulvic acid adsorbs less isoproturon due to the enhanced solubility of the soil organic matter. In alkaline conditions the negatively charged solute and the surface repel each other and the hydrophobic interactions are also weaker than in neutral media.     

The effects of dissolved organic matter and pH on sampling rates for polar organic chemical integrative samplers (POCIS)

The effect of solution pH and levels of dissolved organic matter (DOM) on the sampling rates for model pharmaceuticals and personal care products (PPCPs) and endocrine disrupting substance (EDS) by polar organic chemical integrative samplers (POCIS) was investigated in laboratory experiments. A commercially available POCIS configuration containing neutral Oasis HLB (hydrophilic-lipophilic balance) resin (i.e. pharmaceutical POCIS) and two POCIS configurations prepared in-house containing MAX and MCX anion and cation exchange resins, respectively were tested for uptake of 21 model PPCPs and EDS, including acidic, phenolic, basic and neutral compounds. Laboratory experiments were conducted with dechlorinated tap water over a pH range of 3, 7 and 9. The effects of DOM were studied using natural water from an oligotrophic lake in Ontario, Canada (i.e. Plastic Lake) spiked with different amounts of DOM (the concentration of dissolved organic carbon ranged from 3 to 5 mg L⁻¹ in uptake experiments). In experiments with the commercial (HLB) POCIS, the MCX-POCIS and the MAX-POCIS, the sampling rates generally increased with pH for basic compounds and declined with pH for acidic compounds. However, the sampling rates were relatively constant across the pH range for phenols with high pKa values (i.e. bisphenol A, estrone, estradiol, triclosan) and for the neutral pharmaceutical, carbamazepine. Thus, uptake was greatest when the amount of the neutral species in solution was maximized relative to the ionized species. Although the solution pH affected the uptake of some model ionic compounds, the effect was by less than a factor of 3. There was no significant effect of DOM on sampling rates from Plastic Lake. However, uptake rates in different aqueous matrixes declined in the order of deionized water > Plastic Lake water > dechlorinated tap water, so other parameters must affect uptake into POCIS, although this influence will be minor. MAX-POCIS and MCX-POCIS showed little advantage over the commercial POCIS configuration for monitoring in natural waters.     

Effects of organic matter content and composition on ammonium adsorption in lake sediments

The nature of the influence of organic matter (OM) on ammonium adsorption in lake sediments remains disputed. In this study, the kinetics and thermodynamics of ammonium adsorption were investigated on sediment samples with different OM contents (ignoring the effects of OM mineralization) previously collected from Lake Wuli, a northern bay of Lake Taihu, a shallow lake in southern China. The mechanisms of ammonium adsorption in these samples were characterized by Fourier transform infrared spectrometry and scanning electron microscopy. The results show that the ammonium adsorption capacity of the sediments is highly correlated with their OM content and with the humic content of the OM. The ammonium adsorption capacity of OM varies with its composition, i.e., with the surface properties of the different functional groups present. Indeed, humic acid was found to have a greater ammonium adsorption capacity by itself than when mixed with kerogen and black carbon, the mixture of the latter two components proving a better adsorbent than pure black carbon.     

Effects of organic matter on the distribution of uranium in soil and plant matrices

This work studied interactions of uranium with pure organic compounds, such as glutathione, and more complex mixtures, such as humic acid and aqueous plant extracts. High performance liquid chromatography with UV absorption interfaced to inductively coupled plasma mass spectrometry sequential detection was used to detect organouranium complexes in a variety of soils and plant materials, indicating that nearly 100% of the uranium extracted from certain plant tissues was bound to organic ligands. In addition, soil sorption experiments indicated that humic acid generally decreased uranium sorption to soils and promoted subsequent desorption of uranium because of uranium partitioning to the organic phase. These experiments demonstrate that organic compounds influence the mobility and chemistry of uranium in the environment.     

Dissolved organic matter in pore water of freshwater sediments: effects of separation procedure on quantity, quality and functionality

Pore water was separated either with or without water extraction prior to centrifugation (7600 or 20 000 × g) in order to investigate the effects of separation procedure on the amount and properties of dissolved organic matter (DOM i.e. the material passing through a 0.45-μm filter) in three freshwater sediments. On the basis of solubility in alkaline, organic matter was concluded to compose of humic substances in two (S1 and S3) and of humin (S2) in one of the sediments. DOM in the samples was quantified by total organic carbon measurement. Specific UV-absorption (SUVA) and high performance size exclusion chromatography (HPSEC) analyses were used to characterize DOM. Sorption of pyrene was used as a measure for functionality of DOM. Both water extraction and centrifugation speed were shown to affect the properties of DOM; however, the effects were sediment dependent. Water extraction increased the amount of DOM separated from the two sediments that had humic character (S1 and S3). In most cases water extraction increased SUVA and shifted the molecular size distribution of DOM towards larger sizes. The separation procedure had also an effect on the functionality of DOM. In water extracted samples of S2 and S3 the sorption of pyrene was higher than in the corresponding samples separated without water extraction, whereas in S1 similar effect was not found. Generally, centrifugation speed had smaller effects on the properties of DOM than water extraction. The fact that the effects of separation procedure on DOM depend on the sediment characteristics complicates the comparison between samples and evaluation of functionality in field conditions.     

Heavy metals and arsenic fixation into freshwater organic matter under Gammarus pulex L. influence

Organic sediments are a main sink for metal pollutants in aquatic systems. However, factors that make sediments a sink of metals and metalloids are still not clear. Consequently, we investigate the role of invertebrate shredders (Gammarus pulex L.) on quality of metal and arsenic fixation into organic partitions of sediment in the course of litter decay with laboratory microcosm experiments. During the decomposition of leaf litter, G. pulex significantly facilitated the development of small particles of organic matter. The capacity of metal fixation was significantly higher in smaller particles than leaf litter and litter residuals. Thus, G. pulex enhanced metal fixation into the organic partition of sediments by virtue of increasing the amount smaller particles in the aquatic system. Furthermore, invertebrates have a significant effect on formation of dissolved organic matter and remobilization of cobalt, molybdenum and cesium, but no significant effect on remobilization of all other measured elements.     

Differentiating with fluorescence spectroscopy the sources of dissolved organic matter in soils subjected to drying

The relative fluorescence, normalised on dissolved organic carbon (DOC), and a humification index, based on the location of the fluorescence emission spectra, were used to investigate the possible sources of the increase in dissolved organic matter (DOM) when a soil is dried. From these 2 parameters it could be seen that air drying resulted in a minor increase of more humified material in DOM while the effect of oven drying was mainly due to cell lysis.     

Effects of pH, organic acids, and inorganic ions on lead desorption from soils

The desorption characteristics of lead in two variable charge soils (one developed from Arenaceous rock (RAR) and the other derived from Quaternary red earths (REQ)) were studied, and the effects of pH value, organic acid, and competitive ions were examined. Desorption of Pb(2+) decreased from nearly 100.0 to 20.0% within pH 1.0-4.0 in both soils, and then the decrease diminished at pH > 4.0. Organic ligands at relatively low concentrations (< or =10(-3) mol L(-1)) slightly inhibited Pb(2+) desorption, but enhanced Pb(2+) desorption at higher concentrations. In this study, citric acid or acetic acid at higher concentrations (>10(-3) mol L(-1)) had the greatest improvement of Pb(2+) desorption, followed by malic acid; and the smallest was oxalic acid. Desorption of the adsorbed Pb(2+) increased greatly with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Pb(2+) desorption more than Zn(2+) at the same loading.     

Effects of pH, organic acids, and competitive cations on mercury desorption in soils

The effects of pH, organic acids, and competitive cations on Hg(2+) desorption were studied. Three representative soils for rice production in China, locally referred to as a yellowish red soil (YRS), purplish clayey soil (PCS), and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were, respectively, collected from Jiaxin County, Deqing County, and Xiasha District of Hangzhou City, Zhejiang Province. Most of the added Hg(2+) was adsorbed at low initial concentrations (<2 mg l(-1)). Desorption of the adsorbed Hg(2+) in 0.01M KCl (simulating soil solution) was minimal, but was significantly enhanced by the change of pH, and the presence of organic acids or competitive cations. The desorption of Hg(2+) in the soils decreased with pH from 3.0 to 5.0, leveled off at pH 5.0-8.0, but increased with pH from 7.0 to 9.0. The presence of organic ligands enhanced Hg(2+) desorption in the soils except for YRS, in which the addition of tartaric, malic, or oxalic acid reduced Hg(2+) desorption at low concentrations (<10(-4)M), but Hg(2+) desorption generally increased with organic acid concentration. Citric acid was most effective in increasing Hg(2+) desorption, followed by tartaric acid and malic acid; and oxalic acid was the least effective. Desorption of adsorbed Hg(2+) increased with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Hg(2+) desorption more than Zn(2+) at the same loading rate. CAPSULE: The effects of organic acids and competitive cations on Hg desorption in soil-water system are related to their concentrations, basic chemical properties, and soil properties.     

Effect of natural organic matter and green microalga on carboxyl-polyethylene glycol coated CdSe/ZnS quantum dots stability and transformations under freshwater conditions

The influence of pH, ionic strength, presence of humic or alginic acids, extracellular polymeric substances (EPS), or freshwater microalga Chlorella kesslerii on the stability and transformation of carboxyl-PEG-CdSe/ZnS core/shell quantum dots (QDs) in terms of number, hydrodynamic size and fluorescence of individual particles, was studied by fluorescence correlation spectroscopy. Obtained results demonstrated that QDs form stable dispersions at nanomolar concentrations under conditions typical for freshwaters. The presence of 5 or 15 mg C L⁻¹ of humic acid or 50 mg C L⁻¹ EPS did not significantly affect these parameters. In contrast, 5 or 50 mg C L⁻¹ alginate at ionic strength of 10 mM shifted the hydrodynamic radius toward larger values, suggesting a possible capture of QDs by the linear alginate chains. The addition of microalga to the QD dispersions resulted in a slight reduction of the number of QDs and a significant decline in the fluorescence of individual QDs.     

Effect of organic fertilizers derived dissolved organic matter on pesticide sorption and leaching

Incorporation of organic fertilizers/amendments has been, and continues to be, a popular strategy for golf course turfgrass management. Dissolved organic matter (DOM) derived from these organic materials may, however, facilitate organic chemical movement through soils. A batch equilibrium technique was used to evaluate the effects of organic fertilizer-derived DOM on sorption of three organic chemicals (2,4-D, naphthalene and chlorpyrifos) in USGA (United States Golf Association) sand, a mixed soil (70% USGA sand and 30% native soil) and a silt loam soil (Typic Fragiochrept). DOM was extracted from two commercial organic fertilizers. Column leaching experiments were also performed using USGA sand. Sorption experiments showed that sorption capacity was significantly reduced with increasing DOM concentration in solution for all three chemicals. Column experimental results were consistent with batch equilibrium data. These results suggest that organic fertilizer-derived DOM might lead to enhanced transport of applied chemicals in turf soils.     

Impact of aquaculture on distribution of dissolved organic matter in coastal Jeju Island,Korea, based on absorption and fluorescence spectroscopy

Environmental Science and Pollution Research - In Jeju Island, multiple land-based aquafarms were fully operational along most coastal region. However, the effect of effluent on distribution and...     

Quantifying interactions between propranolol and dissolved organic matter (DOM) from different sources using fluorescence spectroscopy

Beta blockers are widely used pharmaceuticals that have been detected in the environment. Interactions between beta blockers and dissolved organic matter (DOM) may mutually alter their environmental behaviors. To assess this potential, propranolol (PRO) was used as a model beta blocker to quantify the complexation with DOM from different sources using the fluorescence quenching titration method. The sources of studied DOM samples were identified by excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration analysis. The results show that PRO intrinsic fluorescence was statically quenched by DOM addition. The resulting binding constants (log K _oc) ranged from 3.90 to 5.20, with the surface-water-filtered DOM samples claiming the lower log K _oc and HA having the highest log K _oc. Log K _oc is negatively correlated with the fluorescence index, biological index, and the percent fluorescence response (P _i,n) of protein-like region (P _I,n) and the P _i,n of microbial byproduct-like region (P _II,n) of DOM EEMs, while it is correlated positively with humification index and the P _i,n of UVC humic-like region (P _III,n). These results indicate that DOM samples from allochthonous materials rich in aromatic and humic-like components would strongly bind PRO in aquatic systems, and autochthonous DOM containing high protein-like components would bind PRO more weakly.     

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 K(d)=0.056-0.180 J cm(-1); UV-B K(d)=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.     

Ozonation effects on emerging micropollutants and effluent organic matter in wastewater: characterization using changes of three-dimensional HP-SEC and EEM fluorescence data

The degradation of effluent organic matter (EfOM) in a municipal wastewater treated by ozonation was characterized using the methods of high-performance size-exclusion chromatography (HP-SEC) and excitation/emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC). The removal of 40 diverse trace-level contaminants of emerging concern (CEC) present in the wastewater was determined as well. Ozonation caused a rapid decrease of the absorbance and fluorescence of the wastewater, which was associated primarily with the oxidation of high and low apparent molecular weight (AMW) EfOM fractions. PARAFAC analysis also showed that components C1 and C2 decreased prominently in these conditions. The EfOM fraction of intermediate molecular weight ascribable to a terrestrial humic-like component (C3) tended to be less reactive toward ozone. Relative changes of EEM fluorescence were quantified using F _max values of PARAFAC-identified components (∆F/F ⁰ _max). Unambiguous relationships between ∆F/F ⁰ _max values and the extent of the degradation of the examined CECs (∆C/C₀) were established. This allowed correlating main parameters of the ∆C/C₀ vs. ∆F/F ⁰ _max relationships with the rates of oxidation of these CECs. The results demonstrate the potential of online measurements of EEM fluorescence for quantitating effects of ozonation on EfOM and micropollutants in wastewater effluents.