Natural and experimental structural evolution of dispersed organic matter in mudstones: The Shimanto accretionary complex,southwest Japan

Structural changes induced by thermal maturation of dispersed organic matter (OM) in the Shimanto accretionary complex, southwest Japan, were investigated using micro‐Fourier‐transform infrared spectroscopy and micro‐Raman spectroscopy. Natural dispersed OM exhibits systematic structural changes inferred from D1‐ and G‐band FWHM values, Raman band separation (RBS), and intensity ratios of the D1‐ and G‐bands (I_D1/I_G ratio) from diagenetic zone to anchizone (IC values: 0.75–0.30). Infrared spectra indicate a loss of aliphatic CH _x, aromatic CH _x, and oxygen‐containing structures as temperature increases. These changes are consistent with discontinuities in thermal structures bounded by out‐of‐sequence thrusts. Kinetic pyrolysis experiments indicate that the I_D1/I_G ratio of synthesized OM has a power law relationship with heat treatment time. Kinetic models of temperature dependence were fitted using the I_D1/I_G ratio, and an effective activation energy of 106 ±17 kJ/mol was estimated using an Arrhenius equation. The activation energies estimated by power law rate and Avrami models have a least‐square correlation coefficient of 0.93, indicating the temperature dependence of carbonization. The estimated effective activation energy is consistent with that of coal, lignin, cellulose, and hemicellulose during thermal degradation. On the other hand, RBS, and D1‐ and G‐band FWHM values of OM display more complex changes with increasing heating temperature and time, and it is difficult to constrain rate parameters during pyrolysis experiments. Our data indicate that the I_D1/I_G ratio is controlled by a simple thermally activated process, whereas RBS and D1‐ and G‐band FWHM values can be affected by lithostatic pressure, fluid activity, hydrogen index, and host lithology, as well as temperature. Structural evolution of dispersed OM in mudstones differs between natural and anhydrous closed experimental systems. Natural carbonization based on micro‐Raman spectroscopy should be applied for a limited indicator of thermal maturation, especially for dispersed OM in diagenetic zone.     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

Study of the Interaction Mechanism in the Biosorption of Copper(II) Ions onto Posidonia oceanica and Peat

A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption–desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4–6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q_max) at pH 6 of 85.78 and 49.69 mg g^?1, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO₃)₂, and EDTA was applied to copper‐saturated biosorbents. Around 65–70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH₂, and CH₃ in aliphatic structures, COO^? and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si? O groups on the surface of peat. The results of SEM‐EDX and FTIR analysis of copper‐saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption–desorption processes affected the thermal stability of the biosorbents.     

Characterization of Organic Contaminants in New York/New Jersey Harbor Sediments Using FTIR‐ATR and Synchrotron FTIR

Dredging and remediation of contaminated Harbor sediments requires characterization of organic pollutants. In this paper, we apply a combination of Fourier transform IR attenuated total reflectance (FTIR‐ATR) and synchrotron FTIR techniques to the investigation of sediments and related materials from New York/New Jersey Harbor and other locations. The FTIR techniques give information on the functional groups of the compounds found in the sediments and make possible measurements with a spatial resolution of about 0.015 mm. Comparisons of natural organic materials namely, river and groundwater humic substances, recent marine and lacustrine sediments, and ancient sedimentary kerogen show that contaminated NY/NJ Harbor sediments display a strong and distinct absorption in their IR spectra at 2850–2950 cm^?1 identified as a C? H stretching band, indicative of the presence of anthropogenic hydrocarbons. We suggest that the presence of this band could be used for rapid screening for the presence of contaminant organic compounds in sediments encountered in dredging operations and/or as an indicator for the efficacy of sediment decontamination technologies used for treatment of dredged material.     

Determination of critical shear stress of non‐cohesive soils using submerged jet test and turbulent kinetic energy

Laboratory tests using Jet Erosion Testing (JET) apparatus, impinging normally on a horizontal boundary, were conducted to determine the critical shear stress (τ_c) of non‐cohesive soil samples. A three‐dimensional (3D) SonTek/YSI 16 MHz Micro‐Acoustic Doppler Velocimeter (MicroADV) was used to measure turbulent kinetic energy (TKE) at a radial limit of entrainment in the wall jet zone and the measurements were used to calculate τ_c of the samples. The results showed that TKE increases exponentially with increasing particle size. The τ_c from this study were comparable (R² = 0.8) to the theoretical τ_c from Shields diagram after bed roughness scale ratio (D/k_s), due to the non‐uniform bed conditions, was accounted for. This study demonstrated that JET and TKE can be used to determine τ_c of non‐cohesive soils. The use of JET and TKE was found to be faster and easier when compared to the conventional approach of using flumes. A relationship of TKE at the onset of incipient motion (TKE_c) and samples’ D₅₀ developed in this study can be used to predict τ_c of non‐cohesive soils under similar non‐uniform conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

A novel ATR‐FTIR technique for identifying colloid composition in natural waters

Although understanding colloid composition has been frequently cited as essential to predicting contaminant transport in natural waters, most current methods to collect and identify colloid composition chemically alter the colloids prior to analysis and fail to identify colloid mineralogy and organic components. This paper presents a new, low‐cost method employing attenuated total reflection Fourier transform infrared spectroscopy (ATR‐FTIR) to identify colloids including organic material in concentrated suspensions. The concentration method employing tangential ultrafiltration at a steady temperature prevents redistribution of dissolved phase and suspended sediments into the colloidal fraction through post‐sampling reactions. ATR‐FTIR allows for direct analysis of concentrated suspensions rather than requiring drying that may alter composition in the colloidal phase, for example, by precipitating carbonates in samples from karst waters. The ability of this technique to monitor variation in colloidal composition is demonstrated through the examination of colloids under two different flow conditions in a karst aquifer and the West Branch of the Susquehanna River in Central Pennsylvania. Copyright © 2014 John Wiley & Sons, Ltd.     

A Study: Removal of Cu(II), Cd(II), and Pb(II) Ions from Real Industrial Water and Contaminated Water Using Activated Sludge Biomass

This study aims to remove of Cu²⁺, Cd²⁺, and Pb²⁺ ions from solution and to investigate the adsorption isotherms, adsorption kinetics, and ion‐exchange affinities of these metals using waste activated sludge (AS) biomass. The adsorptions of the metals on biomass were optimal at an acidic pH value of 6.0 based on its monolayer capacities. Maximum monolayer capacities of AS biomass (q_max) were calculated as 0.478, 0.358, and 0.280 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺, respectively, and the adsorption equilibrium time was found as 60 min for each metal. The adsorbed amount of metal rose with increasing of initial metal ion concentration. The equilibrium adsorption capacity of AS for initial 0.25 mmol L^?1 metal concentration was determined as 0.200, 0.167, and 0.155 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺ ions, respectively. These relevant values were determined as 0.420, 0.305, and 0.282 mmol g^?1 for Cu²⁺, Cd²⁺, and Pb²⁺ ions, respectively, when initial metal concentration was 0.50 mmol L^?1. In the multi‐metal sorption system, the adsorption capacity of AS biomass was observed in the order of Cu²⁺ > Cd²⁺ > Pb²⁺. In the presence of 100 mmol L^?1 H⁺ ion, the order of ion‐exchange affinity with H⁺ was found as Cu²⁺ > Cd²⁺ > Pb²⁺. The adsorption kinetics were also found to be well described by the pseudo‐second‐order and intraparticle diffusion models. Two different rate constants were obtained as k_i1 and k_i2 and k_i1 (first stage) was found to be higher than k_i2 (second stage).     

Characterisation of Fulvic Acids and Glycyrrhizic Acid by Time‐of‐Flight Secondary Ion Mass Spectrometry

Fulvic acids of different origin, spray deposited on polished silicon after dissolution in high‐purity water without any additives, were analysed by time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) in combination with oblique 24...36 keV SF₅⁺ ion bombardment. The observed, highly reproducible mass spectra cover more than five orders of magnitude in dynamic range, without background subtraction. Apart from lines due to atomic ions and low‐mass ion fragments, the mass spectra exhibit broad maxima between m/z 200...350, mainly due to a beat‐like superposition of lines at every single mass number, up to at least m/z 400. In the negative ion spectra the beats have a spacing of m/z 14, corresponding to a CH₂‐unit. The high‐mass tails of the spectra extend well beyond m/z 5000, with similar slopes in the positive and the negative ion mass spectra. The negative spectra appear to be less affected by fragmentation products than the positive spectra. Fulvic acids (FAs) of different origin show distinctly different spectra, with mean masses ranging between m/z ≈ 450 and 580 (for a low‐mass cut‐off m/z 150). To further verify the ability of TOF‐SIMS to detect molecules and clusters with masses significantly above the maxima of the FA spectra, samples of glycyrrhizic acid (GA, as GA ammonium salt with molecular weight 840) were also analysed. Parent ions as well as multimers (GA)_n were observed as positive and negative ions, up to n = 4 (m/z 3320). The results are compared with spectra recently obtained by other mass spectrometric techniques.     

Sorption of ortho‐Phenylphenol to Soils

Conflicting sorption coefficients for ortho‐phenylphenol (OPP) have been reported in the literatures, which resulted in the conflicting assessments on OPP mobility in soil. To ascertain the sorption coefficient of OPP, batch experiments were performed based on OECD guideline 106, using three types of soils. Headspace solid‐phase microextraction (HS‐SPME) and GC‐MS were applied to the determination of OPP concentration in the liquid phase. The sorption isotherms obtained for all three soils under equilibrium conditions were described well, assuming linear sorption. The organic carbon normalized distribution coefficients (K_oc) ranged from 894 to 1703 L kg^?1, which suggested that OPP is moderately mobile in soil. The results also showed that the K_oc value of OPP can be predicted precisely from K_ow, whereas it was underestimated by one order of magnitude when water solubility is used.     

Changes in carbon and nitrogen cycling in a floodplain lake over recent decades linked to littoral expansion,declining riverine influx,and eutrophication

This study aimed to understand changes in the biogeochemical processing of organic matter (OM) in response to multiple stressors (e.g., littoral area expansion, wastewater input, and hydrological regulation) in East Dongting Lake (Central China) over the past 60 years, using analyses of total organic carbon (TOC), total nitrogen (TN), C/N ratios, δ¹³C, δ¹⁵N, and diatoms from 2 sediment cores collected from the littoral and central parts of the lake. OM mainly originated from phytoplankton and C₃ plant‐derived soil OM based on the ranges of C/N ratios (from 7 to 11) and δ¹³C (between ?27‰ and ?23‰). Littoral area expansion due to siltation caused an increasing influx of terrestrial soil OM in the 1980s and the 1990s, subsequently lowering δ¹³C values and rising C/N ratios in both sediment cores. Meanwhile, higher δ¹⁵N was linked to a high influx of isotopically heavy nitrate from urban and agricultural wastewaters. After 2000, slight decreases in TOC and TN in the littoral area were attributable to reducing inputs of external OM, likely linked to declining sediment influx from the upper reaches resulting from the Three Gorges Dam impoundment. Contrasting increases in TOC, TN, and C/N ratios in the central part indicated a high influx of terrestrial soil OM due to the declining distance from the shoreline with littoral area expansion. Declining δ¹⁵N values after 2000 indicated an increase in N₂‐fixing cyanobacteria with eutrophication. Changes in diatom assemblages in both the littoral and central zones reflected nutrient enrichment and hydrological alterations. These results indicate that littoral expansion, declining riverine influx, and anthropogenic nutrient inputs are potential driving forces for the biogeochemical processing of OM in floodplain lakes. This study provides sedimentary biogeochemical clues for tracking past limnological conditions of floodplain lakes that are subjected to increasing disturbances from hydrological regulation and eutrophication.     

Efficiency of Pleurotus florida Laccase on Decolorization and Detoxification of the Reactive Dye Remazol Brilliant Blue R (RBBR) under Optimized Conditions

Laccase from the white‐rot fungus Pleurotus florida, produced under solid‐state fermentation conditions, was used for the decolorization of reactive dye Remazol Brilliant Blue R (RBBR). RBBR was decolorized up to 46% by P. florida laccase alone in 10 min. In the presence of N‐hydroxybenzotriazole (HBT), the rate of decolorization was enhanced 1.56‐fold. Central composite design of response surface methodology with four variables namely, dye, enzyme, redox mediator concentrations, and time at five levels was applied to optimize the RBBR decolorization. The predicted optimum level of variables for maximum RBBR decolorization (87%) was found to be 52.90 mg L^?1 (RBBR), 1.87 U mL^?1 (laccase), 0.85 mM (HBT), and 7.17 min (time), respectively. The validation results showed that the experimental value of RBBR decolorization (82%) was close to the predicted one. The disappearance of C–N and C–X groups, and a small shift in N–H groups in Fourier‐transform infra red (FTIR) spectroscopy confirms the degradation of RBBR chromophore by laccase enzyme. The phytotoxicity of RBBR was considerably reduced after the treatment with laccase. RBBR decolorization kinetics; K_m and V_max were calculated to be 145.82 mg L^?1 and 24.86 mg L^?1 min, respectively.     

Separation and Preconcentration of Boron with a Glucamine Modified Novel Magnetic Sorbent

A novel, simple method based on magnetic separation was developed for analytical purposes. In this method, N‐methyl‐D‐glucamine (NMDG) modified magnetic microparticles that were synthesized by using the sol‐gel method were used for the selective extraction and preconcentration of boron from aqueous solutions. This method combines the simplicity and selectivity of solvent extraction with the easy separation of magnetic microparticles from a solution with a magnet without any preliminary filtration step. The structure of the prepared γ‐Fe₂O₃‐SiO₂‐NMDG (magnetic sorbent) composites were characterized by using X‐ray diffraction (XRD), Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FTIR). The influence of different parameters on the sorbent capacity, such as the sorption/desorption of boron, magnetic sorbent dosage, pH, equilibrium time, type, and amount of stripping solution, were evaluated by using the magnetic sorbent. Any equilibrium pH greater than 6 can be used for sorption. Desorption from the sorbent was carried out by using 1.0 M HCl. The sorption and desorption efficiency of the γ‐Fe₂O₃‐SiO₂‐NMDG was found as 92.5 ± 0.5% and 99.8 ± 6%, respectively.     

Characterization of Estuarine and Fluvial Dissolved Organic Matter by Thermochemolysis using Tetramethylammonium Hydroxide

Selected samples of dissolved organic matter (DOM) isolated by ultrafiltration (UDOM) have been analyzed by thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). This technique cleaves ester and ether bonds of bio‐ and geological macromolecules and releases monomer subunits and methylates them in situ as their methyl ethers and methyl esters. Compared with conventional pyrolysis, TMAH thermochemolysis avoids decarboxylation of preexisting carboxylic moieties and produces aromatic acids as their methyl esters. Various phenolic derivatives, which might originate from incorporated lignin‐derived structures, from the highly aliphatic and resistant biopolymer cutan and also from proteinaceous materials, were identified among the products produced from UDOM upon thermochemolysis. The presence of lignin derivatives in UDOM indicates input of organic matter derived from terrestrial sources. Various aromatic acids, perhaps representing the final steps in the oxidation of the side‐chain during microbial oxidation of lignin, were released upon TMAH thermochemolysis, suggesting they are structural constituents of the UDOM. Different ratios of lignin‐derived materials, commonly determined using the CuO oxidation method, such as the Δ value, indicative of the amount of lignin present, the acid/aldehyde ratio (Ad/Al)_G, indicative of the extent of oxidative degradation of the lignin component, and the syringyl/guaiacyl (S/G) and p‐hydroxyphenyl/guaiacyl (P/G) ratios, indicative of the contribution for the different types of lignin, were determined.     

Hydraulic properties of peat soils along a bulk density gradient—A meta study

Our understanding of hydraulic properties of peat soils is limited compared with that of mineral substrates. In this study, we aimed to deduce possible alterations of hydraulic properties of peat soils following degradation resulting from peat drainage and aeration. A data set of peat hydraulic properties (188 soil water retention curves [SWRCs], 71 unsaturated hydraulic conductivity curves [UHCs], and 256 saturated hydraulic conductivity [K_s] values) was assembled from the literature; the obtained data originated from peat samples with an organic matter (OM) content ranging from 23 to 97 wt% (weight percent; and according variation in bulk density) representing various degrees of peat degradation. The Mualem‐van Genuchten model was employed to describe the SWRCs and UHCs. The results show that the hydraulic parameters of peat soils vary over a wide range confirming the pronounced diversity of peat. Peat decomposition significantly modifies all hydraulic parameters. A bulk density of approximately 0.2 g cm^?3 was identified as a critical threshold point; above and below this value, macroporosity and hydraulic parameters follow different functions with bulk density. Pedotransfer functions based on physical peat properties (e.g., bulk density and soil depth) separately computed for bog and fen peat have significantly lower mean square errors than functions obtained from the complete data set, which indicates that not only the status of peat decomposition but also the peat‐forming plants have a large effect on hydraulic properties. The SWRCs of samples with a bulk density of less than 0.2 g cm^?3 could be grouped into two to five classes for each peat type (botanical composition). The remaining SWRCs originating from samples with a bulk density of larger than 0.2 g cm^?3 could be classified into one group. The Mualem‐van Genuchten parameter values of α can be used to estimate K_s if no K_s data are available. In conclusion, the derived pedotransfer functions provide a solid instrument to derive hydraulic parameter values from easily measurable quantities; however, additional research is required to reduce uncertainty.     

Synthesis of soil‐hydraulic properties and infiltration timescales in wildfire‐affected soils

We collected soil‐hydraulic property data from the literature for wildfire‐affected soils, ash, and unburned soils. These data were used to calculate metrics and timescales of hydrologic response related to infiltration and surface runoff generation. Sorptivity (S) and wetting front potential (Ψ_f) were significantly different (lower) in burned soils compared with unburned soils, whereas field‐saturated hydraulic conductivity (K_fs) was not significantly different. The magnitude and duration of the influence of capillarity during infiltration was greatly reduced in burned soils, causing faster ponding times in response to rainfall. Ash had large values of S and K_fs but moderate values of Ψ_f, compared with unburned and burned soils, indicating ash has long ponding times in response to rainfall. The ratio of S²/K_fs was nearly constant (~100 mm) for unburned soils but more variable in burned soils, suggesting that unburned soils have a balance between gravity and capillarity contributions to infiltration that may depend on soil organic matter, whereas in burned soils the gravity contribution to infiltration is greater. Changes in S and K_fs in burned soils act synergistically to reduce infiltration and accelerate and amplify surface runoff generation. Synthesis of these findings identifies three key areas for future research. First, short timescales of capillary influences on infiltration indicate the need for better measurements of infiltration at times less than 1 min to accurately characterize S in burned soils. Second, using parameter values, such as Ψ_f, from unburned areas could produce substantial errors in hydrologic modeling when used without adjustment for wildfire effects, causing parameter compensation and resulting underestimation of K_fs. Third, more thorough measurement campaigns that capture soil‐structural changes, organic matter impacts, quantitative water repellency trends, and soil‐water content along with soil‐hydraulic properties could drive the development of better techniques for numerically simulating infiltration in burned areas.     

Ultrasonic velocities of North Sea chalk samples: influence of porosity, fluid content and texture

We have studied 56 unfractured chalk samples of the Upper Cretaceous Tor Formation of the Dan, South Arne and Gorm Fields, Danish North Sea. The samples have porosities of between 14% and 45% and calcite content of over 95%. The ultrasonic compressional‐ and shear‐wave velocities (V_P and V_S) for dry and water‐saturated samples were measured at up to 75 bar confining hydrostatic pressure corresponding to effective stress in the reservoir. The porosity is the main control of the ultrasonic velocities and therefore of the elastic moduli. The elastic moduli are slightly higher for samples from the South Arne Field than from the Dan Field for identical porosities. This difference may be due to textural differences between the chalk at the two locations because we observe that large grains (i.e. filled microfossils and fossil fragments) that occur more frequently in samples from the Dan Field have a porosity‐reducing effect and that samples rich in large grains have a relatively low porosity for a given P‐wave modulus. The clay content in the samples is low and is mainly represented by either kaolinite or smectite; samples with smectite have a lower P‐wave modulus than samples with kaolinite at equal porosity. We find that ultrasonic V_P and V_S of dry chalk samples can be satisfactorily estimated with Gassmann's relationships from data for water‐saturated samples. A pronounced difference between the V_P/V_S ratios for dry and water‐saturated chalk samples indicates promising results for seismic amplitude‐versus‐offset analyses.     

Impacts of Methane on Carbon Dioxide Storage in Brine Formations

In the context of geological carbon sequestration (GCS), carbon dioxide (CO₂) is often injected into deep formations saturated with a brine that may contain dissolved light hydrocarbons, such as methane (CH₄). In this multicomponent multiphase displacement process, CO₂ competes with CH₄ in terms of dissolution, and CH₄ tends to exsolve from the aqueous into a gaseous phase. Because CH₄ has a lower viscosity than injected CO₂, CH₄ is swept up into a ‘bank’ of CH₄‐rich gas ahead of the CO₂ displacement front. On the one hand, this may provide a useful tracer signal of an approaching CO₂ front. On the other hand, the emergence of gaseous CH₄ is undesirable because it poses a leakage risk of a far more potent greenhouse gas than CO₂ if the cap rock is compromised. Open fractures or faults and wells could result in CH₄ contamination of overlying groundwater aquifers as well as surface emissions. We investigate this process through detailed numerical simulations for a large‐scale GCS pilot project (near Cranfield, Mississippi) for which a rich set of field data is available. An accurate cubic‐plus‐association equation‐of‐state is used to describe the non‐linear phase behavior of multiphase brine‐CH₄‐CO₂ mixtures, and breakthrough curves in two observation wells are used to constrain transport processes. Both field data and simulations indeed show the development of an extensive plume of CH₄‐rich (up to 90 mol%) gas as a consequence of CO₂ injection, with important implications for the risk assessment of future GCS projects.     

Quantitation of Nonextractable Anthropogenic Quantitation of Nonextractable Anthropogenic Sediments after Chemical Degradation

Four highly contaminated sediment samples obtained from three sampling locations of the Teltow Canal, Berlin, were investigated by quantitation of extractable and nonextractable organic contaminants. The selection of the anthropogenic contaminants (including chlorinated and brominated naphthalenes, 2, 4, 6‐tribromoaniline, phthalates, tri‐n‐butylphosphate, 2, 2, 4‐trimethyl‐1, 3‐pentanediol diisobutyrate, bisphenol A, butylated nitrophenols, 4‐nitrobenzoic acid, galaxolide, and tonalide) based on the results of extended GC‐MS screening analyses applied to the extracts of the sediment samples as well as to the extracts derived from selective chemical degradation procedures. In detail, alkaline hydrolyses, BBr₃‐treatment and RuO₄‐oxidation were applied to the pre‐extracted sediment samples in both a separate and a sequential mode.     

Optimization and Modeling of the Photocatalytic Degradation of the Insect Repellent DEET in Aqueous TiO2 Suspensions

Response surface methodology (RSM) and artificial neural networks (ANNs) based on a multivariate central composite design (CCD) were applied to model and optimize the photocatalytic degradation of N,N‐diethyl‐m‐toluamide (DEET). The individual and interaction effects of three main operating factors (mass of TiO₂, initial DEET concentration, and irradiation intensity) on process efficiency were estimated, proving their important effect on % DEET removal. Among the independent variables, TiO₂ concentration displayed the highest effect on DEET degradation followed by initial DEET concentration and UV intensity. The optimization and prediction capabilities of ANNs and RSM were compared on the basis of root mean squared error, mean absolute error, absolute average deviation, and correlation coefficient values. Results proved the usefulness and capability of the experimental design strategy for successful investigation and modeling of the photocatalytic process. Moreover, the selected ANN gave better estimation capabilities throughout the range of variables than RSM. Based on the models and the related experimental conditions, the optimal values of each parameter were determined. Under optimum conditions, DEET and total organic carbon (TOC) followed pseudo‐first order kinetics. Nearly complete degradation of DEET took place within 15 min whereas high TOC removal percentages (>85%) was achieved after 90 min irradiation time.     

Performance of A Combination Process of UV/H2O2/Micro‐Aeration for Oxidation of Dichloroacetic Acid in Drinking Water

The decomposition of dichloroacetic acid (DCAA) in water using a UV/H₂O₂/micro‐aeration process was investigated in this paper. DCAA cannot be removed by UV radiation, H₂O₂ oxidation or micro‐aeration alone, while UV/H₂O₂/micro‐aeration combination processes have proved effective and can degrade this compound completely. With initial concentrations of about 110 μg/L, more than 95.1% of DCAA can be removed in 180 min under UV intensity of 1048.7 μW/cm², H₂O₂ dosage of 30 mg/L and micro‐aeration flow rate of 2 L/min. However, more than 30 μg/L of DCAA was left after 180 min by UV/H₂O₂ combination process without micro‐aeration with the same UV intensity and H₂O₂ dosage. The effects of applied UV radiation intensity, H₂O₂ dose, initial DCAA concentration and pH on the degradation of DCAA have been examined in this study. Degradation mechanisms of DCAA with hydroxyl radical oxidation have been discussed. The removal rate of DCAA was sensitive to operational parameters. There was a linear relationship between rate constant k and UV intensity and initial H₂O₂ concentration, which indicated that a higher removal capacity can be achieved by improvement of both factors. A newly found nitrogenous disinfection by‐product (N‐DBP)‐DCAcAm, which has the potential to form DCAA, was easier to remove than DCAA by UV/H₂O₂ and UV/H₂O₂/micro‐aeration processes. Finally, a preliminary cost comparison revealed that the UV/H₂O₂/micro‐aeration process was more cost‐effective than the UV/H₂O₂ process in the removal of DCAA from drinking water.