Adsorbed and Bound Residues in Fulvic Acid Fractions of a Contaminated Groundwater – Isolation:, Chromatographic and Spectroscopic Characterization

Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.     

Biodegradation of Nonylphenol Ethoxylate Surfactants in Biofilm Reactors

The primary degradation of a technical nonylphenol ethoxylate surfactant with an average chain length of 10 ethoxylate units (NPEO‐10) was studied in a flow‐through system by means of miniaturized biofilm reactors (mBFR) with bacteria from an activated sludge plant. 5 mg/L of the test compound (total EO concentration) were spiked in synthetic wastewater (SWW) and fed to the reactors continuously for 64 days. Compound removal and the formation of degradation products (DP) were monitored under both oxic and anoxic conditions. Solid‐phase extraction and RP‐HPLC with fluorescence detection were employed for sample preparation and analysis. Better removal of the parent compound was seen with the oxic reactors (50 to 70%) than with the anoxic reactors (30 to 50%). Compared to SWW organic matter, the test compound proved to be of refractory nature. The appearance of degradation products in the effluent was earlier with anoxic reactors despite their lower elimination efficiency. After extraction of biomass only minor amounts of NPEO‐10 and metabolites were found, indicating that small amounts were present in adsorbed or intracellular form. Ultimate biodegradation of NPEO‐10 and of octylphenol ethoxylates (OPEO‐9.5; average chain length of 9.5 EO units) was tested by means of manometric respirometry at a theoretical oxygen demand (ThOD) of 100 mg/L. Whereas NPEO‐10 was biodegraded by only 26%, at best, in 28 days, OPEO‐9.5 degradation amounted to (40 ± 5)%.     

An Approach for Classification of Groundwaters by Synchronous Fluorescence Spectroscopy and Discriminant Analysis

Monitoring and evaluation of groundwater quality in drinking water protectorates is of particular interest if the uncontrolled entry of pollutants, for example by infiltrating river water, cannot be excluded. A fluorescence spectroscopic method is presented as possible alternative to the conventional expensive hydrochemical investigations. This method uses the information yielded by synchronous fluorescence spectra. After a Fourier transformation of the original spectra and a following discriminant analysis, the samples can be classified in different groups corresponding to the different types of groundwater. The method was tested in the drinking water protectorate of a waterworks of a German metropolis (Halle, Sachsen-Anhalt). We found a prediction rate of about 90% in the investigated case.     

Enhanced red fluorescence emission in the oxygen minimum zone of the Arabian Sea

 Depth profiles of fluorescence at several excitation and emission wavelengths were measured along with CTD data during the cruise So119 of RV Sonne in the Arabian Sea from 12 May to 10 June 1997. In addition to chlorophyll fluorescence from phytoplankton in the near-surface layer, the profiles in the oxygen minimum region well below the euphotic zone show enhanced red fluorescence. Red fluorescence intensity is inversely related to the oxygen concentration in intermediate and deep waters. A relationship to characteristic water masses of the region cannot be found in the data, and this holds also with chemical data such as DOC. Absorbance spectra of water samples taken in the oxygen minimum zone show an absorption band at 420 nm wavelength with about 50 nm bandwidth, much weaker than gelbstoff absorbance in the same wavelength range. The absorption band remains stable after sample filtration with 0.45 μm glass fibre filters. Hence, the size of the absorbing matter is in the range of dissolved molecules or particles much smaller than 1 μm. Fluorescence spectra of unfiltered samples with 420 nm excitation show a weak emission band at 600 nm and a more pronounced one at 660 nm wavelength. The trailing edge of the 660 nm band falls into the range of chlorophyll emission, thus giving rise to the observed depth profiles of red fluorescence in the oxygen minimum zone. Red fluorescence measured on samples remain stable during a few hours after sampling even in the presence of oxygen. It is not detectable after several weeks of sample storage in the dark and cannot be reproduced even after depletion of dissolved oxygen. Received: 22 May 2002 / Accepted: 18 February 2003 Responsible Editor: Andreas Oschlies Acknowledgements. This work was supported by a grant from the Federal Minister of Education and Technology, Bonn, within the frame work of the JGOFS Arabian Sea program. We are grateful to the captain and the crew of RV Sonne for their support. We are indebted to Mrs. Kirsten Neumann from the Institute of Marine Chemistry and Biogeochemistry of the University of Hamburg for providing the oxygen data, and to Mr. Nikolai Delling from the same institute for making the DOC and chlorophyll data available to us.     

Fluorescence as a Tool for Tracing the Organic Contamination from Pulp Mill Effluents in Surface Waters

Three‐dimensional fluorescence spectra of water samples from an eucalyptus bleached kraft pulp mill and from a river, upstream and downstream of the discharge of the effluent, revealed the existence of a peak at δ_exc = 280 nm and δ_em = 340 nm Δδ = 60 nm), characteristic of effluentπs organic matter. Humic substances were isolated from the effluent by sequential adsorption onto resins XAD‐8 and XAD‐4 in series. Their synchronous fluorescence spectra with Δδ = 60 nm do also exhibit an intense signal at δ_exc = 280 nm (≈ 300 nm in the humic acid fraction). The peak is absent in the spectra of humic substances isolated from a non‐polluted site of the river, but it is clearly seen in the spectra of the humic substances from a site downstream of the discharge of the effluent. Synchronous fluorescence spectra (Δδ = 60 nm) of water samples from the river and its lagoon were recorded and revealed to be an easy and fast way of tracing the organic contamination from the effluent.     

Differences between Humic Substances from Riverine,Estuarine, and Marine Environments Observed by Fluorescence Spectroscopy

Sixteen samples of fulvic acids and XAD‐4 fractions of riverine, estuarine, coastal, and open ocean origin have been studied by emission and synchronous molecular fluorescence spectroscopy. Certain features of the molecular fluorescence are related to the nature, the content, and the origin of those aquatic humic substances (HS). Riverine HS appear several times richer in fluorophores than marine HS, which can be well observed by emission fluorescence spectroscopy. Synchronous‐scan spectra of fulvic acids and of XAD‐4 fractions from the aquatic environments studied, emphasized the quality differences of their fluorophores. These features are useful as tracers of humic substances related with their natural environment source or even with their anthropogenic origin.     

Spectroscopic investigation of humic substances in a tropical lake during a complete hydrological cycle

Fluorescence and UV‐VIS techniques were employed for the investigation of natural organic matter (NOM) of a tropical lake. The relationships of absorbance/dissolved organic carbon (A/DOC), fluorescence intensity/dissolved organic carbon (FI/DOC), fluorescence ratio (FR), and peak wavelength with the highest intensity (PW) were used to distinguish the pedogenic or aquagenic origin of NOM. The values of FR, PW and A₂₈₅/DOC of high waters (HW) or flooded period samples and of low waters (LW) period samples of the dry season, except for September 2002, confirm the predominance of pedogenic material. The spectra of water were similar to the standard fulvic acid (FA), and the spectra of FA from the lake were similar to the nearby soils, indicative of pedogenic predominance. The results confirm that the dissolved NOM of Patos Lagoon – MS (Brazil), in all sampling periods, predominantly consisted of humic substances (FA) of pedogenic origin.     

Effects of sewage discharges on lipid and fatty acid composition of the Patagonian bivalve Diplodon chilensis

Lipid and fatty acid (FA) composition and selected oxidative stress parameters of freshwater clams (Dipolodon chilensis), from a sewage-polluted (SMA) and a clean site, were compared. Trophic markers FA were analyzed in clams and sediment. Saturated FA (SAFA), and bacteria and sewage markers were abundant in SMA sediments, while diatom markers were 50% lower. Proportions of SAFA, branched FA, 20:5n − 3 (EPA) and 22:6n − 3 (DHA) were higher in SMA clams. Chronic exposure of D. chilensis to increasing eutrophication affected its lipid and FA composition. The increase in EPA and DHA proportions could be an adaptive response, which increases stress resistance but could also lead to higher susceptibility to lipid peroxidation TBARS, lipofuscins (20-fold) and GSH concentrations were higher in SMA clams. FA markers indicated terrestrial plant detritus and bacteria are important items in D. chilensis diet. Anthropogenic input in their food could be traced using specific FA as trophic markers.     

Continuous Multi‐probe Measurements in Fastflowing Waters Using a Hydrographic Slot

Taking continuous spatiotemporal in situ measurements with multi‐probes in fast‐flowing waters/rivers can be problematic because the sensors may be damaged by high shear forces and flotsam. To protect the multi‐probe and to enable easy access for the maintenance and calibration of the sensors, a special multi‐probe holder fixed in a hydrographic slot was developed. The validation of the probe system revealed a “memory effect” at short time scales (< 10 s) within sharp gradients caused by the overflow container of the multi‐probe rack keeping the sensors submerged in the sample water. Continuously recorded data (conductivity, temperature, pH, oxygen concentration and saturation, as well as in vivo fluorescence of chlorophyll‐a) from a research cruise on board the RV ALBIS along the river Elbe (river km 309) and entering the river Saale are presented. This river stretch upstream of the city of Magdeburg to the mouth of the Saale tributary was found to have a complex physicochemical character, which is attributable to the long mixing process of water from the river Saale and the river Elbe.     

Fluorophores in the Arabian Sea and their relationship to hydrographic conditions

 Water mass distributions, upwelling and filament formation are of complex significance for biological and chemical processes. Temperature and salinity are routinely used to characterize these hydrographic conditions. In situ profiles and sample analyses from the cruise So119 of RV Sonne in May 1997 into the Arabian Sea indicate that optical parameters such as the fluorescence of phytoplankton pigments, gelbstoff and proteins reflect hydrographic processes as well, and are useful to describe and explain biochemical processes. The dependence of bio-optical parameters to DOC and chlorophyll a concentrations is examined. While the relation between extracted chlorophyll and chlorophyll fluorescence is quite reasonable, DOC and gelbstoff fluorescence do not show a functional dependency. This is mainly due to sunlight-induced degradation of fluorophores in the surface layer. Enhanced gelbstoff signals in intermediate and deep waters are related to Persian Gulf Water. The optical data reveal a relation between the depth of the chlorophyll maximum, the depth of 1% surface light and the geographical latitude. In the context of remote sensing of phytoplankton biomass from ocean colour images, the depth of the chlorophyll maximum is a crucial parameter. Thus, the revealed dependency on latitude is useful for the evaluation of primary production with satellite remote sensing. Received: 22 May 2002 / Accepted: 18 February 2003 Responsible Editor: Andreas Oschlies Acknowledgements. This work was supported by a grant from the Federal Minister of Education and Technology, Bonn, within the framework of the JGOFS Arabian Sea program. We are grateful to the captain and the crew of RV Sonne for their support. Special thanks are given to the chief scientist of the cruise, Pr. V. Ittekkot, for helpful discussions. We are indebted to Mr. Rüdiger Heuermann and Mr. Nils Bürckel for their participation in the cruise and their support in the data analysis.     

Characteristics and role of groundwater dissolved organic matter on arsenic mobilization and poisoning in Bangladesh

The fluorescence and molecular weight characteristics of dissolved organic matter (DOM) in groundwater of Bangladesh were investigated to evaluate its multiple roles on arsenic (As) mobilization and poisoning. Fluorescence properties of DOM were measured in groundwater samples collected from two As contaminated areas of Bangladesh (Faridpur at the Ganges floodplain and Sonargaon at the Meghna floodplain) from different locations and depths. The three dimensional excitation–emission matrix (3DEEM) fluorescence spectra of groundwater samples showed two characteristic peaks around Ex/Em = 335–365 nm/435–480 nm for fulvic-like peaks and peak at around Ex/Em = 275–290 nm/310–335 nm for the protein-like materials. The similarity of fluorescence spectra of groundwater and surface water of both the study areas with high intensity of fluorescence and its strong correlation with DOC reflect the in situ generation of fluorescent DOM from sedimentary organic matter (SOM) and recent recharge of terrestrial labile organic carbon into shallow aquifer. High performance size-exclusion chromatography (HPSEC) analysis of DOM shows positive correlations between fluorescence intensities (FI) of small molecular fractions (0.65 kDa) and As concentrations, with the signatures of protein-like peaks of DOM in groundwater. This result provides new evidence that small molecular weight fraction of DOM in groundwater of Bangladesh can play an important role on As mobilization and toxicity. In addition, high concentration of fluorescence materials in DOM of As contaminated groundwater of Bangladesh may pose a threat to public health.     

Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM)

To explore whether quinone moieties are important in chromophoric dissolved organic matter (CDOM) photochemistry in natural waters, hydrogen peroxide (H₂O₂) production and associated optical property changes were measured in aqueous solutions irradiated with a Xenon lamp for CDOM model compounds (dihydroquinone, benzoquinone, anthraquinone, napthoquinone, ubiquinone, humic acid HA, fulvic acid FA). All compounds produced H₂O₂ with concentrations ranging from 15 to 500 μM. Production rates were higher for HA vs. FA (1.32 vs. 0.176 mM h⁻¹); values ranged from 6.99 to 0.137 mM h⁻¹ for quinones. Apparent quantum yields (Θ_app; measure of photochemical production efficiency) were higher for HA vs. FA (0.113 vs. 0.016) and ranged from 0.0018 to 0.083 for quinones. Dihydroquinone, the reduced form of benzoquinone, had a higher production rate and efficiency than its oxidized form. Post-irradiation, quinone compounds had absorption spectra similar to HA and FA and 3D-excitation–emission matrix fluorescence spectra (EEMs) with fluorescent peaks in regions associated with CDOM.     

Non-destructive assessment of polycyclic aromatic hydrocarbon (PAH) exposure by fluorimetric analysis of crab urine

The detection of urinary polycyclic aromatic hydrocarbon (PAH) metabolites by fluorescence spectrophotometry is particularly effective as a practical means to assess PAH exposure in decapod crabs. However, the practical application of this technique has thus far only been tested for the European shore crab (Carcinus maenas) and only a few field studies have been conducted in heavily polluted areas. The present study evaluated the adaptability of this method as a rapid, cost-effective and non-destructive biomonitoring tool for the New Zealand crab species, Macrophthalmus hirtipes (stalk-eyed mud crab). A field gradient could be detected among the sites and different input sources of PAH contamination could be discerned through the differentiation of pyrogenic and petrogenic PAH signatures. The present study shows that the fluorescence screening method is sensitive to relatively low levels of PAH contamination and more broadly applicable to smaller crab species than C. maenas, for which the technique was developed.     

The effects of coal gangue and fly ash on the hydraulic properties and water content distribution in reconstructed soil profiles of coal‐mined land with a high groundwater table

Soil water systems have been severely degraded in coal‐mined and subsiding land, where a shallow groundwater table is also present. The present paper discussed the effects of fly ash (FA) and coal gangue (CG) as filling materials on the hydraulic properties and water content distribution in a profile for the purpose of rehabilitating subsided lands. The saturated water content, water characteristic curve, and water diffusivity of local soil, FA, CG, and a mixture of FA and CG (“mixed filling”) were characterized. A column experiment was conducted to investigate the changes of water content in profiles reconstructed from the combination of soil and filling materials, including soil only, FA, CG, and a mixture of FA and CG, which were used to fill the lower part of the reconstructed profile. The mixture of FA and CG was found to possess similar hydraulic properties to those of the soil, particularly high water‐holding capacity and permeability. Moreover, the volumetric water contents in the whole profile containing the mixture of FA and CG were consistent with those of the profile reconstructed with soil only. As a result, it is recommended to adopt the mixture of FA and CG for reconstructing the lower profile of the land to alleviate or rehabilitate subsided land in coal mines.     

Comparisons of picophytoplankton abundance, size, and fluorescence between summer and winter in northern South China Sea

The abundance, size, and fluorescence of picophytoplankton cells were investigated during the summer (July-August of 2009) and winter (January of 2010) extending from near-shore coastal waters to oligotrophic open waters in northern South China Sea, under the influence of contrasting seasonal monsoons. We found that the median abundance of Prochlorococcus averaged over top 150 m decreased nearly 10 times in the winter compared to the summer in the whole survey area, while median abundance of Synechococcus and picoeukaryotes increased 2.6 and 2.4 folds, respectively. Vertical abundance profiles of picoeukaryotes usually formed a subsurface maximum during the summer with the depth of maximal abundances tracking the depth of nutricline, whereas their vertical distributions were more uniform during the winter. Size and cellular fluorescence of Prochlorococcus and Synechococcus usually increased with depth in the summer, while the size of picoeukaryotes was smallest at the depth of maximal abundances. Size, cellular fluorescence, and chlorophyll-to-carbon ratio of Prochlorococcus and Synechococcus in surface waters were generally higher in the winter than in the summer and onshore than offshore, probably resulting from different temperature, nutrient, and light environments as well as different ecotype compositions. Prochlorococcus cells were most abundant in warm and oligotrophic environments, while the abundance of Synechococcus and picoeukaryotes was the highest in waters with intermediate chlorophyll and nutrient concentrations. The distributional patterns of picophytoplankton groups are consistent with their specific physiology documented in previous studies and can be possibly predicted by environmental physical and chemical variables.     

Optical signatures of dissolved organic matter in the watershed of a globally large river (Yangtze River,China)

Parallel factor analysis of fluorescence excitation emission matrices of surface water samples of a globally large river (Yangtze River, China) watershed identified three classes of fluorescent dissolved organic matter (FDOM) that had ex/em = 280/330 nm, 305/385 nm and 350/450 nm respectively, resembling “peak T”, “peak M” and “peak C” commonly identified in natural water, respectively. Peak T (a tyrosine/tryptophan-like FDOM) did not show correlations to peak M or C which were humic-like substances, while a positive correlation (r = 0.935, p < 0.001) was present between the natural log-transformed maximum fluorescence intensity (F_max) of peaks T and M indicating a tight link during their production and processing. F_max values (in Raman unit nm^?1) normalized to dissolved organic carbon (DOC) concentration were low, varying in ranges 15.93–85.95, 29.83–83.54 and 19.73–51.05 × 10^?5 nm^?1 (μmol/L)^?1 for peaks T, M and C, respectively, in line with the history of strong photobleaching of the water samples as indicated by fairly high absorption spectral slope ratios (0.75–1.53 with a mean 1.03). Intermediate fluorescence index (FI) (1.46–1.83 with a mean 1.61) and small specific absorption at 254 nm (0.64–1.93 with a mean 1.15 m^?1 mg^?1 L) of the water samples, indicated the presence of both aquatic microbial DOM (e.g. peak T) and soil DOM (e.g. peak C). Peak C could be substantially removed by UV-A (320–400 nm) irradiation, while peak M was slightly increased when a microbe-containing water was exposed to the same UV-A irradiation. Taken together, peak C was attributed to diffuse soil source while peak M was likely attributed to joint effects of microbial activities and solar irradiation on the chromophores in the sample.     

Time-series modeling of reservoir effects on river nitrate concentrations

Saylorville Reservoir is a 24.1 km² impoundment of the Des Moines River located approximately 10 km north of the City of Des Moines, Iowa, USA. Surface water from the Des Moines River used for drinking water supply is impaired for nitrate–nitrogen. Monthly mean nitrate concentration data collected upstream and downstream of the reservoir for a 30-year period (1977–2006) were selected for time-series analysis. Our objectives were to (1) develop a model describing nitrate concentrations downstream of the reservoir as a function of the concentrations entering the reservoir and (2) use the model to provide a 1-month ahead forecast for downstream water quality. Results indicated that downstream nitrate can be effectively modeled using a transfer function approach that utilized inflow concentrations during the current and previous month as input variables. Inflow concentrations were modeled using an AR(20) model, with the higher order model consistent with temporal correlation noted by others. The transfer function model suggested that the reservoir is reducing nitrate concentrations by 22 ± 6%, a reduction that greatly exceeds previous estimates. Monthly nitrate forecasted with the model were nearly all within a 95% prediction interval of their actual measured values and did not appear greatly affected by flow variations.     

Accumulation of Heavy Metals by Chickpea Grown in Fly Ash Treated Soil: Effect on Antioxidants

Chickpea grown in fly ash (FA) treated soil (25, 50, and 100% FA) was used to evaluate the effect of FA on antioxidants, metal concentration (Fe, Zn, Cu, Cr, and Cd), photosynthetic pigments (chlorophyll a (chl‐a), chlorophyll b (chl‐b), total chlorophyll (total chl), and carotenoids), growth and yield performance. All antioxidants in roots, shoots and leaves of chickpea increase with increasing FA doses to combat FA stress. The activities of antioxidants were more in the root tissues to cope with stress induced in the plants as compared to shoot and leaf. Concentration of metals was found maximum in roots than the shoots and seeds. The highest concentration of Fe and lowest level of Cd were recorded in all treatments of FA for different parts of the plant. The treated crop showed reduced level of chlorophyll but enhanced level of carotenoids and protein. However, root length, number of nodules and biomass in 25 and 50% FA treatments did not differ significantly in comparison to respective control plants. These results suggest that heavy metals of FA causes oxidative stress in this crop and the antioxidant enzymes could help a pivotal role against oxidative injury.     

Composition of in situ burn residue as a function of weathering conditions

Troll B crude oil was weathered under Arctic conditions with different ice coverage: open water, 50% ice and 90% ice. Samples (100 mL) were taken during the experiment and tested for ignitability in a burning cell. From each burning a residue sample was taken for analysis. The burning process removed the light compounds eluting before C13. No effect from the prior weathering time or the different ice coverage was seen in the burn residue composition. The content of selected Poly Aromatic Hydrocarbons (PAHs) was determined and it was noted that the concentration of PAHs with more than 4 rings were increased. The source origin of the PAHs was investigated by use of relative ratios of PAH isomers and indicated that some formation of PAHs was additionally taking place during burning.