Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Preconcentration by Coprecipitation of Copper and Nickel with Mo(VI)/Triazole Derivative System and Their Determinations by Flame Atomic Absorption Spectrometry in Food and Water Samples

A new separation and preconcentration technique based on coprecipitation of Cu(II) and Ni(II) ions by the aid of Mo(VI)/di‐tert‐butyl{methylenebis[5‐(chlorobenzyl)‐4H‐1,2,4‐triazol‐3,4‐diyl]}biscarbamate (BUMECTAC) precipitate has been established. The Mo(VI)/BUMECTAC precipitate was dissolved by concentrated HNO₃ and the solution was completed to 5.0 mL with distilled/deionized water. The levels of the analyte ions were determined by flame atomic absorption spectrometer. The effects of experimental conditions like HNO₃ concentration, amount of BUMECTAC and Mo(VI), sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of analyte ions. The preconcentration factors were found to be 40 for Cu(II) and 100 for Ni(II) ions. The detection limits for Cu(II) and Ni(II) ions based on 3σ (N:10) were 0.43 and 0.70 µg L^?1, respectively. The relative standard deviations were found to be lower than 4.0% for both analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of two certified reference materials (Environment Canada TM‐25.3 and CRM‐SA‐C Sandy Soil C). The procedure was successfully applied to sea water and stream water as liquid samples and baby food as solid sample in order to determine the levels of Cu(II) and Ni(II) ions.     

Modelling and experimental study of coupled exchange of p,p′‐DDE and colloids in a flume simulated stream–streambed system

Stream–subsurface exchange plays a significant role in the fate and transport of contaminants in streams. It has been modelled explicitly by considering fundamental processes such as hydraulic exchange, colloid filtration, and contaminant interactions with streambed sediments and colloids. The models have been successfully applied to simulate the transport of inorganic metals and nutrients. In this study, laboratory experiments were conducted in a recirculating flume to investigate the exchange of a hydrophobic organic contaminant, p,p′‐dichloro‐diphenyl‐dichloroethane (DDE), between a stream and a quartz sand bed. A previously developed process‐based multiphase exchange model was modified by accounting for the p,p′‐DDE kinetic adsorption to and desorption from the bed sediments/colloids and was applied to interpret the experimental results. Model input parameters were obtained by conducting independent small‐scale batch experiments. Results indicate that the immobilization of p,p′‐DDE in the quartz sand bed can occur under representative natural stream conditions. The observed p,p′‐DDE exchange was successfully simulated by the process‐based model. The model sensitivity analysis results show that the exchange of p,p′‐DDE can be sensitive to either the sediment sorption/desorption parameters or colloidal parameters depending on the experimental conditions tested. For the experimental conditions employed here, the effect of colloids on contaminant transport is expected to be minimal, and the stream–subsurface exchange of p,p′‐DDE is dominated by the interaction of p,p′‐DDE with bed sediment. The work presented here contributes to a better mechanistic understanding of the complex transport process that hydrophobic organic contaminants undergo in natural streams and to the development of reliable, predictive models for the assessment of impacted streams. Copyright © 2015 John Wiley & Sons, Ltd.     

Bestimmung von Atrazin,Terbutylazin und ihrer Desethyl- sowie Hydroxymetaboliten in Boden mittels SFE und HPLC/UV-DAD

Determination of Atrazine, Terbutylazine and their Deethyl- and Hydroxymetabolites in Soil by SFE and HPLC/UV-DAD The supercritical fluid extraction (SFE) (CO₂ and CH₃OH as modifier) of the herbicides atrazine and terbutylazine as well as their deethyl- and hydroxymetabolites from soil was investigated. The analytes were determined after extraction by HPLC/UV-DAD using a C18 column. The limits of detection of the chromatographic step were between 0.01 μg/mL and 0.07 μg/mL, the relative standard deviations between 0.8% and 1.4%. With the aid of a control chart, the stability of the chromatographic system was evaluated. For extraction, soil was spiked with 5 μg/g for each component. For SFE, CO₂ and methanol as modifier were used, and a pressure program was applied. Beside SFE, Soxhlet extraction with methanol and a solid-liquid extraction with acetone/water by shaking were carried out. For chlorine-containing triazines, the recovery rates were comparable for all extraction methods. The following recovery rates for SFE were obtained: deethylterbutylazine 77.4%, terbutylazine 80.2%, deethylatrazine 87.4%, atrazine 92.6%. However, the recovery rates for the hydroxymetabolites (4.1% for hydroxyatrazine, 21% for hydroxyterbutylazine) were not satisfying compared with the “classical” methods of extraction (above 50%). The limits of detection for the total process (SFE and HPLC/UV-DAD) estimated by the signal to noise ratio amounted 0.08 μg/g soil for chlorine-containing derivates, for hydroxyatrazine 2…3 μg/g, and for hydroxyterbutylazine 0.8 μ/g.     

Seasonal rainfall–runoff relationships in a lowland forested watershed in the southeastern USA

Hydrological processes of lowland watersheds of the southern USA are not well understood compared to a hilly landscape due to their unique topography, soil compositions, and climate. This study describes the seasonal relationships between rainfall patterns and runoff (sum of storm flow and base flow) using 13 years (1964–1976) of rainfall and stream flow data for a low‐gradient, third‐order forested watershed. It was hypothesized that runoff–rainfall ratios (R/P) are smaller during the dry periods (summer and fall) and greater during the wet periods (winter and spring). We found a large seasonal variability in event R/P potentially due to differences in forest evapotranspiration that affected seasonal soil moisture conditions. Linear regression analysis results revealed a significant relationship between rainfall and runoff for wet (r² = 0·68; p < 0·01) and dry (r² = 0·19; p = 0·02) periods. Rainfall‐runoff relationships based on a 5‐day antecedent precipitation index (API) showed significant (r² = 0·39; p < 0·01) correspondence for wet but not (r² = 0·02; p = 0·56) for dry conditions. The same was true for rainfall‐runoff relationships based on 30‐day API (r² = 0·39; p < 0·01 for wet and r² = 0·00; p = 0·79 for dry). Stepwise regression analyses suggested that runoff was controlled mainly by rainfall amount and initial soil moisture conditions as represented by the initial flow rate of a storm event. Mean event R/P were higher for the wet period (R/P = 0·33), and the wet antecedent soil moisture condition based on 5‐day (R/P = 0·25) and 30‐day (R/P = 0·26) prior API than those for the dry period conditions. This study suggests that soil water status, i.e. antecedent soil moisture and groundwater table level, is important besides the rainfall to seasonal runoff generation in the coastal plain region with shallow soil argillic horizons. Copyright © 2011 John Wiley & Sons, Ltd.     

Residual drift demands in moment‐resisting steel frames subjected to narrow‐band earthquake ground motions

This paper presents the main results of the evaluation of residual inter‐story drift demands in typical moment‐resisting steel buildings designed accordingly to the Mexican design practice when subjected to narrow‐band earthquake ground motions. Analytical 2D‐framed models representative of the study‐case buildings were subjected to a set of 30 narrow‐band earthquake ground motions recorded on stations placed in soft‐soil sites of Mexico City, where most significant structural damage was found in buildings as a consequence of the 1985 Michoacan earthquake, and scaled to reach several levels of intensity to perform incremental dynamic analyses. Thus, results were statistically processed to obtain hazard curves of peak (maximum) and residual drift demands for each frame model. It is shown that the study‐case frames might exhibit maximum residual inter‐story drift demands in excess of 0.5%, which is perceptible for building's occupants and could cause human discomfort, for a mean annual rate of exceedance associated to peak inter‐story drift demands of about 3%, which is the limiting drift to avoid collapse prescribed in the 2004 Mexico City Seismic Design Provisions. The influence of a member's post‐yield stiffness ratio and material overstrength in the evaluation of maximum residual inter‐story drift demands is also discussed. Finally, this study introduces response transformation factors, T_p, that allow establishing residual drift limits compatible with the same mean annual rate of exceedance of peak inter‐story drift limits for future seismic design/evaluation criteria that take into account both drift demands for assessing a building's seismic performance. Copyright © 2013 John Wiley & Sons, Ltd.     

Plant Species Mediate Rhizosphere Microbial Activity and Biodegradation Dynamics in a Riparian Soil Treated with Bensulfuron‐methyl

A pot experiment was conducted to investigate microbial characteristics and the biodegradation process of bensulfuron‐methyl (BSM) in a rhizosphere soils planted with different riparian plants. The results showed that microbial population decreased with BSM addition in the rhizosphere, especially for bacteria and fungi. The activities of the dehydrogenase (DHase) were stimulated firstly, due to BSM addition, but then were inhibited, and recovered to the initial level, while the activities of the phosphatase and urease showed obviously decreasing trend throughout the whole experiment. Rhizosphere soil substrate‐induced respiration (SIR) was depressed by BSM, especially at the initial 14 days of incubation. Compared to Zizania aquatica and Phragmites australis, Acorus calamus showed a significantly (p < 0.05) higher DHase activity and larger SIR in the rhizosphere soils treated with BSM, which means that A. calamus can effectively alleviate inhibitory effect of the sulfonylurea herbicide addition on microbial activity. There were significant (p < 0.05) differences in microbial degradation dynamics of BSM in the rhizosphere soils among three kinds of riparian plants. A. calamus displayed a significantly (p < 0.05) higher degradation efficiency of BSM in the rhizosphere soils, followed by Z. aquatica and P. australis. The residual BSM concentration in A. calamus rhizosphere soil was 23.1 and 32.2% lower than that in Z. aquatica and P. australis rhizosphere soils, respectively, indicating a greater improvement effect on biodegradation of BSM in A. calamus rhizosphere soils.     

Atmospheric Concentrations and Phase Partitioning of Polycyclic Aromatic Hydrocarbons in Izmir,Turkey

Ambient air polycyclic aromatic hydrocarbon (PAH) samples were collected at a suburban (n = 63) and at an urban site (n = 14) in Izmir, Turkey. Average gas‐phase total PAH (∑₁₄PAH) concentrations were 23.5 ng m^?3 for suburban and 109.7 ng m^?3 for urban sites while average particle‐phase total PAH concentrations were 12.3 and 34.5 ng m^?3 for suburban and urban sites, respectively. Higher ambient PAH concentrations were measured in the gas‐phase and ∑₁₄PAH concentrations were dominated by lower molecular weight PAHs. Multiple linear regression analysis indicated that the meteorological parameters were effective on ambient PAH concentrations. Emission sources of particle‐phase PAHs were investigated using a diagnostic plot of fluorene (FLN)/(fluorine + pyrene; PY) versus indeno[1,2,3‐cd]PY/(indeno[1,2,3‐cd]PY + benzo[g,h,i]perylene) and several diagnostic ratios. These approaches have indicated that traffic emissions (petroleum combustion) were the dominant PAH sources at both sites for summer and winter seasons. Experimental gas–particle partition coefficients (K_P) were compared to the predictions of octanol–air (K_OA) and soot–air (K_SA) partition coefficient models. The correlations between experimental and modeled K_P values were significant (r² = 0.79 and 0.94 for suburban and urban sites, respectively, p < 0.01). Octanol‐based absorptive partitioning model predicted lower partition coefficients especially for relatively volatile PAHs. However, overall there was a relatively good agreement between the measured K_P and soot‐based model predictions.     

Morphology of riffle–pool sequences in the River Severn,England

Despite the occurrence of riffle–pool sequences in many rivers there are few data concerning riffle–pool unit morphology. Of many criteria proposed to identify riffle–pool units, only three methods can be regarded as objective and robust. These are the ‘zero‐crossing’, the ‘spectral analysis’ and the ‘control‐point’ methods. In this paper statistics are developed using the first two of these methods to describe the streamwise morphology of 275 riffles and 285 pools which form a continuous 32·1 km reach of the bed of the River Severn in Shropshire, England. Yalin's theoretical relationship between the average riffle:pool unit length ( λ _p) and channel width ( W ), λ _p = 3 W , applies to the River Severn. Reach‐average riffle height ( H ) is a constant proportion of bankfull depth ( h ); typically H ≅ 0·16 h . Riffle height is a positive function of riffle length. Pool depth is a positive function of pool length. However, both riffle length and pool length increase more rapidly than the bed‐level amplitude, such that long riffles or pools are relatively ‘flat’. As channel gradient reduces, bedforms flatten and become more asymmetric as riffle stoss sides and the proximal slope of pools lengthen at the expense of riffle lee sides and pool distal slopes. The statistical relationships between riffle steepness (H/L) and water depth are similar to those for equilibrium subaqueous dunes. The Severn data are consistent with Yalin's theoretical analysis relating riffle bedform length (L _r) to water depth, i.e. L _r = α2π h, wherein α ≅ 1 for steep near‐equilibrium bedforms but α ≅ 2 to 3 as the relative depth decreases and riffles become long, low features. Theoretical consideration and turbulence data indicate that the frequency of coherent turbulent‐flow structures associated with the riffle–pool mixing length in the Severn should be of the order of 50 to 100 s. The morphological similarity of the steepest River Severn riffles with dunes raises intriguing questions with respect to self‐similar, convergent organization of periodic alluvial bedforms and to bedform dynamic classification particularly. Copyright © 2000 John Wiley & Sons, Ltd.     

Predicting Diel,Diurnal and Nocturnal Dynamics of Dissolved Oxygen and Chlorophyll‐a Using Regression Models and Neural Networks

Human‐induced and natural interruptions with continuous streams of observational data necessitate the development of gap‐filling and prediction strategies towards better understanding, monitoring and management of aquatic systems. This study quantified the efficacy of multiple non‐linear regression (MNLR) versus artificial neural network (ANN) models as well as the temporal partitioning of diurnal versus nocturnal data for the predictions of chlorophyll‐a (chl‐a) and dissolved oxygen (DO) dynamics. The temporal partitioning increased the predictive performances of the best MNLR models of diurnal DO by 45% and nocturnal DO by 4%, relative to the best diel MNLR model of diel DO ($r_{{\rm adj}}^{2} = 68.8\%$ ). The ANN‐based predictions had a higher predictive power than the MNLR‐based predictions for both chl‐a and DO except for diurnal DO dynamics. The best ANNs based on independent validations were multilayer perceptron (MLP) for diel chl‐a, generalized feedforward (GFF) for diurnal and nocturnal chl‐a, MLP for diel DO, GFF for diurnal DO, and MLP for nocturnal DO.     

Sorption Behaviour of Phenols on Natural Sandy Aquifer Material during Flow‐through Column Experiments: The Effect of pH

Flow‐through column experiments were carried out to investigate the influence of pH on the sorption of three phenols (2‐methyl‐4, 6‐dinitrophenol, 2, 4, 6‐trichlorophenol, pentachlorophenol) onto a natural sandy aquifer material collected from a bank filtration site of River Elbe, Germany. For the phenols investigated, an increase in sorption (retardation) with decreasing pH is observed indicating a stronger sorption of the neutral species in comparison to that of the anions formed by dissociation. The anions of 2‐methyl‐4, 6‐dinitrophenol and 2, 4, 6‐trichlorophenol do not show significant sorption. On the contrary, pentachlorophenol showed sorption not only in neutral form but also in ionic form significantly which should be taken into account while assessing the fate and transport of such compound. A linear model based on the degree of protonation (calculated from pH and pK_a) can be used to resolve the apparent (observed) sorption coefficient (K_{d, app}) into its neutral (K_{d, n}) and ionised (K_{d, i}) components. Knowing pK_a, K_{d, n}, and K_{d, i} the apparent sorption coefficient for pH values other than experimentally investigated can be predicted.     

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.     

Dynamic,Mechanistic, and Thermodynamic Modeling of Zn(II) Ion Biosorption onto Zinc Sequestering Bacterium VMSDCM

The surface of the bacterial cells before the biosorption of Zn(II) ion has been found rough, heterogeneous, and non‐crystalline together with tremendous protrusions and negatively charged functional groups. The bacterium was characterized as rod shaped with Gram‐negative type of cell wall structure. In reaction dynamics, pseudo‐second‐order kinetics with higher linear correlation coefficient (R²) ranging between 0.97 and 0.99, lower sum of square errors (SSE) (0.035–0.081) and chi (χ²) (0.0013–0.009) provided a better explanation of sorption of Zn(II) ion on bacterium surface as compared to pseudo‐first‐order model. The removal of Zn(II) was governed by both film and intra‐particle diffusion at onset and later stage of sorption of metal ion on the surface of bacterial cells. The R² (0.92–0.94) for intra‐particle diffusion model was quite higher with lower values of SSE (9.56–16.33) and chi (χ²) (11.26–19.65) against the Bangham's model. The positive value of ΔH (16.628 × 10^?6 kJ/mol) and ΔS (5320.90 kJ/mol/K) showed that the biosorption of Zn(II) ion across liquid phase on bacterial surface was endothermic with increased randomness at solid–liquid interface. The negative values of ΔG demarcated the whole process as spontaneous in nature. In the present work, the distribution coefficient was found to be > 0.5 at various temperature ranges. At the attainment of equilibrium, the residual concentration of Zn(II) ion in liquid phase was around 0.6 mg/L, which was much below the limit described by United States Environmental Protection Agency (USEPA), i.e. 5 mg/L.     

Searching for similarity in topographic controls on carbon,nitrogen and phosphorus export from forested headwater catchments

Topography influences hydrological processes that in turn affect biogeochemical export to surface water on forested landscapes. The differences in long‐term average annual dissolved organic carbon (DOC), organic and inorganic nitrogen [NO₃^?‐N, dissolved organic nitrogen (DON)], and phosphorus (total dissolved phosphorus, TDP) export from catchments in the Algoma Highlands of Ontario, Canada, with similar climate, geology, forest and soil were established. Topographic indicators were designed to represent topographically regulated hydrological processes that influence nutrient export, including (1) hydrological storage potential (i.e. effects of topographic flats/depressions on water storage) and (2) hydrological flushing potential (i.e. effects of topographic slopes on potential for variable source area to expand and tap into previously untapped areas). Variations in NO₃^?‐N export among catchments could be explained by indicators representing both hydrological flushing potential (91%, p < 0.001) and hydrological storage potential (65%, p < 0.001), suggesting the importance of hydrological flushing in regulating NO₃^?‐N export as well as surface saturated areas in intercepting NO₃^?‐N‐loaded runoff. In contrast, hydrological storage potential explained the majority of variations among catchments in DON (69%, p < 0.001), DOC (94%, p < 0.001) and TDP (82%, p < 0.001) export. The lower explanatory power of DON (about 15% less) compared with that of DOC and TDP suggests another mechanism influencing N export, such as controls related to alternative fates of nitrogen (e.g. as gas). This study shows that simple topographic indicators can be used to track nutrient sources, sinks and their transport and export to surface water from catchments on forest landscapes. Copyright © 2013 John Wiley & Sons, Ltd.     

River discharge,land use change,and surface water quality in the Xiangjiang River,China

To compare the impacts of river discharge on the surface water quality of the Xiangjiang River in China, 12 surface water quality parameters recorded at 31 sampling sites from January 1998 to December 2008 along the river and its main tributaries were analyzed. Significantly higher concentrations of total nitrogen, ammoniacal nitrogen, and total phosphorus, and biochemical oxygen demand were observed during low‐flow periods than during high‐flow periods, implying a higher risk to local residents drinking untreated water during low‐flow periods. Pollution indexes, including the inorganic pollution index and integrated pollution index (IPI), were negatively related to impervious surface area (ISA) and cropland area (CLA) when ISA (CLA) was less than 160 (3000) km². However, the relationship was positive when ISA (CLA) was larger than 160 (3000) km², which provided a reasonable explanation for the observed spatial patterns of water quality. Distinct increasing temporal trends for two kinds of pollution indexes were also found. The annual ISA was significantly related to the rapid degradation of water quality from 1998 to 2008, with correlation coefficient (r) values of 0.816 (p = 0.002) and 0.711 (p = 0.014) for the organic pollution index (OPI) and IPI, respectively. However, annual rainfall was negatively correlated with the two indexes with r values of 0.785 (p = 0.002) and 0.448 (p = 0.093) for OPI and IPI, respectively. Our study highlights that decision makers should be more aware of recent increases in the pollution of the Xiangjiang River, especially at downriver sites and during low‐flow periods. Copyright © 2013 John Wiley & Sons, Ltd.     

Changes in the Level of Proteins,Free Amino Acids and Protease Activities of Clarias batrachus in Response to Sodium meta‐arsenite Intoxication

Increased hazard of arsenic toxicity at many provinces of India causing extensive contamination of their wetlands. To illustrate the consequences of the arsenic menace on the aquatic fauna, a nutritionally important freshwater catfish Clarias batrachus (Linn.) was subjected to the stress of sublethal concentration (1 mg/L; 5% of 96‐h LC₅₀ value) of sodium meta‐arsenite. The alterations induced by the arsenic salt on certain biomolecules (proteins, free amino acids (FAA), and protease activities) in five tissue components (muscle, liver, brain skin, and gills) of the fish using biochemical techniques were estimated. Significant (p < 0.01) decrease in the concentration of proteins in all the tissues (19.74–44.84% in muscles; 3.17–49.39% in liver; 10.05–36.16% in brain; 12.62–52.01% in skin and 7.34–61.69% in gills), and significant (p < 0.01) increase in FAA (6.84–269.89% in muscles; 125.89–358.03% in liver; 1.07–152.90% in brain; 29.31–401.62% in skin and 38.53–165.07% in gills), and protease activities (43.59–183.33% in muscles; 19.52–131.90% in liver; 8.85–46.72% in brain; 33.33–261.53% in skin and 25.39–50.79% in gills) of the exposed fish were observed. This increase in amino acids and enzyme activity point out toward breakdown of protein leading to their depletion.     

Caustics in a periodically layered transversely isotropic medium with vertical symmetry axis

Wave propagation in a finely layered medium is a very important topic in seismic modelling and inversion. Here we analyse non‐vertical wave propagation in a periodically layered transversely isotropic (VTI) medium and show that the evanescent (attenuation) zones in the frequency‐horizontal slowness domain result in caustics in the group velocity domain. These caustics, which may appear for both the quasi‐compressional (qP) and quasi‐shear (qSV) wave surfaces are frequency dependent but display weak dependence at low frequencies. The caustics computed for a specific frequency differ from those observed at the low‐ and high‐frequency limits. We illustrate these caustics with a few numerical examples and snapshots computed for both qP‐ and qSV‐wave types.     

Application of Hydrophobic Interaction Chromatography (HIC) in Water Analysis Anwendung der Hydrophobizitätschromatographie (HIC) in der Wasseranalytik

Dissolved high molecular weight organic substances, like humic substances, can be characterized with regard to their molecular weight distribution using gel filtration chromatography (GFC). In addition, the adsorption properties, for example on activated carbon, can be described, if the substances are separated by hydrophobic interaction chromatography (HIC) in different fractions using a chromatographic column with a hydrophobic matrix. The retention time (Rt) of single chemical substances in this column can be used to characterize the hydrophobicity or hydrophility of each compound as well as of the high molecular weight organic matter. The hydrophobic interaction between the matrix of the column and the dissolved chemical compounds also depends on the hydrophobicity of the gel and the composition of the eluent. Relations between retention times, log P-coefficients (octanol/water partition) and K-values of isotherms on activated carbon (Freundlich equation) were found.     

Application of the Response Surface Method for Optimization of Headspace Liquid Phase Microextraction of Trihalomethanes in Drinking Water

An optimized analysis method based on headspace liquid phase microextraction (HS‐LPME) and gas chromatography coupled with mass spectrometry was proposed for the determination of trihalomethanes (THMs) in drinking water. The response surface method (RSM) was used to optimize the extraction of THMs for analysis by HS‐LPME. The temperature, extraction time and NaCl concentration were found to be important extraction parameters. The coefficient of determination (R²) for the model was 94.97%. A high probability value (P < 0.0001) for the regression indicated that the model had a high level of significance. The optimum conditions were seen to be: temperature 42.0°C, NaCl concentration 0.30 g/mL, and extraction time 28 min. The response variable was the summation of the THMs chromatography peak areas and the reproducibility of this was investigated in five replicate experiments under the optimized conditions. The relative standard deviations (RSD%) of the THMs ranged from 8.0–11.6%. The limits of detection (LODs), based on a signal‐to‐noise ratio (S/N) of three ranged from 0.42–0.78 μg/L, and were lower than the maximum limits for THMs in drinking water established by the WHO.     

Geomorphological control on boulder transport and coastal erosion before,during and after an extreme extra‐tropical cyclone

Extreme wave events in coastal zones are principal drivers of geomorphic change. Evidence of boulder entrainment and erosional impact during storms is increasing. However, there is currently poor time coupling between pre‐ and post‐storm measurements of coastal boulder deposits. Importantly there are no data reporting shore platform erosion, boulder entrainment and/or boulder transport during storm events – rock coast dynamics during storm events are currently unexplored. Here, we use high‐resolution (daily) field data to measure and characterize coastal boulder transport before, during and after the extreme Northeast Atlantic extra‐tropical cyclone Johanna in March 2008. Forty‐eight limestone fine‐medium boulders (n = 46) and coarse cobbles (n = 2) were tracked daily over a 0.1 km² intertidal area during this multi‐day storm. Boulders were repeatedly entrained, transported and deposited, and in some cases broken down (n = 1) or quarried (n = 3), during the most intense days of the storm. Eighty‐one percent (n = 39) of boulders were located at both the start and end of the storm. Of these, 92% were entrained where entrainment patterns were closely aligned to wave parameters. These data firmly demonstrate rock coasts are dynamic and vulnerable under storm conditions. No statistically significant relationship was found between boulder size (mass) and net transport distance. Graphical analyses suggest that boulder size limits the maximum longshore transport distance but that for the majority of boulders lying under this threshold, other factors influence transport distance. Paired analysis of 20 similar sized and shaped boulders in different morphogenic zones demonstrates that geomorphological control affects entrainment and transport distance – where net transport distances were up to 39 times less where geomorphological control was greatest. These results have important implications for understanding and for accurately measuring and modelling boulder entrainment and transport. Coastal managers require these data for assessing erosion risk. © 2016 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.