Langmuir–Blodgett Film of Asymmetric Calix[4]arene Derivative Modified Electrode for Voltammetric Determination of Silver

A new electrochemical voltammetric sensor, Langmuir–Blodgett (LB) film of 25,27‐dimethoxy‐26‐(N‐trichloroacetyl)carbamoyloxy‐p‐tert‐butylcalix[4]arene (DCA) modified GCE (LB_DCA–GCE), was designed and successfully used for recognition and determination of trace amounts of Ag⁺ in water. Under the optimum experimental conditions, the lowest detectable concentration of Ag⁺ reached 1 × 10^?9 mol L^?1. Moreover, LB_DCA–GCE exhibited a well‐defined response relating to the Ag⁺ with good sensitivity, selectivity, reproducibility, and long stability. The recognizing mechanism of LB_DCA–GCE for silver ion in aqueous solution was also discussed. The results show that the size of calixarene cavity may be the predominate factor affecting recognition of calixarene for silver ions.     

Surfactant Enhance DLLME/FO‐LADS: Assay of Malachite Green Level in Aquatic Environment of Trout Fish

Malachite green (MG), a traditional agent used in aquaculture although is not approved; its low cost and high efficacy make illicit use likely. We developed a small‐scale, simple, and sensitive dispersive liquid–liquid microextraction procedure for the assay of trace amounts of MG in aquatic environment of Trout fish. Fiber optic‐linear array detection spectrophotometry with charge‐coupled device detector benefiting from a microcell was used for this purpose. The method is based on enhancement effect of an anionic surfactant on the extraction of MG in to very fine multidroplets of microextraction solvent which made assisted by disperser solvent. Under the optimum conditions, the enrichment factor 77.5 was obtained from a 5‐mL water sample. The calibration graph was linear up to 5 × 10^?7 mol L^?1 with detection limit of 1 × 10^?8 mol L^?1. The relative standard deviation for seven replicate measurements of 4 × 10^?7 and 5 × 10^?8 mol L^?1 of MG were 3.3 and 4.5%, respectively.     

Quantification of Diclofenac in Hospital Effluent and Identification of Metabolites and Degradation Products

In this study the occurrence of diclofenac and sub‐products in effluent emerging from the University Hospital at the Federal University of Santa Maria was investigated. One metabolite was identified and, in aqueous solution, three degradation products. The quantification was conducted by means of HPLC‐DAD, and the determination of metabolite and degradation products by LC–ESI–MS/MS–QTrap. For the HPLC‐DAD method, a 70:30 mixture of methanol/sodium phosphate was used in isocratic mode. For the LC–ESI–MS/MS–QTrap determinations, a mobile phase, where phase A was an ammonium acetate solution 5 × 10^?3 mol L^?1, and phase B was methanol (5 × 10^?3 mol L^?1)/ammonium acetate (9:1, v/v), on gradient mode. The LDs for the HPLC and LC–MS/MS methods, respectively, were 2.5 and 0.02 µg L^?1, the LQs, 8.3 and 0.05 µg L^?1, and the linear range from 10 up to 2000 µg L^?1 and 0.05 up to 10 µg L^?1. As expected, the LC–ESI–MS/MS–QTrap method was more sensitive and less laborious. The metabolite 4′‐hydroxy‐diclofenac was identified. Photolysis was used for the degradation studies and three products of diclofenac were identified (m/z of 214, 286 and 303) in aqueous solution. These results notwithstanding, no degradation products of diclofenac were found in the hospital effluent.     

Assessing DOC export from a Sphagnum‐dominated peatland using δ13C and δ18O–H2O stable isotopes

Dissolved organic carbon (DOC) originating in peatlands can be mineralized to carbon dioxide (CO₂) and methane (CH₄), two potent greenhouse gases. Knowledge of the dynamics of DOC export via run‐off is needed for a more robust quantification of C cycling in peatland ecosystems, a prerequisite for realistic predictions of future climate change. We studied dispersion pathways of DOC in a mountain‐top peat bog in the Czech Republic (Central Europe), using a dual isotope approach. Although δ¹³C_DOC values made it possible to link exported DOC with its within‐bog source, δ¹⁸O_H2O values of precipitation and run‐off helped to understand run‐off generation. Our 2‐year DOC–H₂O isotope monitoring was complemented by a laboratory peat incubation study generating an experimental time series of δ¹³C_DOC values. DOC concentrations in run‐off during high‐flow periods were 20–30 mg L^?1. The top 2 cm of the peat profile, composed of decaying green moss, contained isotopically lighter C than deeper peat, and this isotopically light C was present in run‐off in high‐flow periods. In contrast, baseflow contained only 2–10 mg DOC L^?1, and its more variable C isotope composition intermittently fingerprinted deeper peat. DOC in run‐off occasionally contained isotopically extremely light C whose source in solid peat substrate was not identified. Pre‐event water made up on average 60% of the water run‐off flux, whereas direct precipitation contributed 40%. Run‐off response to precipitation was relatively fast. A highly leached horizon was identified in shallow catotelm. This peat layer was likely affected by a lateral influx of precipitation. Within 36 days of laboratory incubation, isotopically heavy DOC that had been initially released from the peat was replaced by isotopically lighter DOC, whose δ¹³C values converged to the solid substrate and natural run‐off. We suggest that δ¹³C systematics can be useful in identification of vertically stratified within‐bog DOC sources for peatland run‐off.     

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.     

Selective Preconcentration of Trace Amounts of Cu(II) With Surface‐Imprinted Multiwalled Carbon Nanotubes

In this study, a new sorbent is synthesized using surface imprinting technique. Cu(II)‐imprinted multiwalled carbon nanotube sorbent (Cu(II)‐IMWCNT) is used as the solid phase in the solid‐phase extraction method. After the preconcentration procedure, Cu(II) ions are determined by high‐resolution continuum source atomic absorption spectrometry. A total of 0.1 mol L^?1 ethylenediaminetetraacetic acid (EDTA) is used to remove Cu(II) ions from the sorbent surface. The optimum experimental conditions for effective preconcentration of Cu(II), parameters such as pH, eluent type and concentration, flow rate, sample volume, sorbent capacity, and selectivity are investigated. The synthesized solid phase is characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The maximum adsorption capacities of Cu(II)‐IMWCNT and non‐imprinted solid phases are 270.3 and 14.3 mg g^?1 at pH 5, respectively. Under optimum experimental conditions for Cu(II) ions, the limit of detection is 0.07 μg L^?1 and preconcentration factor is 40. In addition, it is determined to be reusable without significant decrease in recovery values up to 100 adsorption–desorption cycles. Cu(II)‐IMWCNT have a high stability. To check the accuracy of the developed method, certified reference materials, and water samples are analyzed with satisfactory analytical results.     

Electro‐Catalytic Degradation of Phenol Organics with SnO2‐Sb2O3/Ti Electrodes

The effect of extraordinary degradation of phenol organics on the SnO₂‐Sb₂O₃/Ti electrode is investigated through experimental research and theoretical analysis. The phenol organics contained 4‐chloro‐phenol, 4‐bromo‐phenol, and 2‐iodo‐phenol. At a current density of 4 mA cm^–2 and an electrolysis time of 12 h, the degradation efficiency of the phenols was over 98% with a relatively short degradation time, whereas the degradation time of the PbO₂/Ti electrode surpassed 40 h while delivering 100% disposal efficiency. Therefore, the effectiveness of electrochemical (EC) oxidation by the SnO₂‐Sb₂O₃/Ti was superior to that of the PbO₂/Ti electrode. At the same time, the SnO₂‐Sb₂O₃/Ti had higher oxygen generation potential and lower electron consumption than the other electrodes. This was mainly due to the effect of the middle Sb₂O₃ layer, which due to its high porosity and good catalytic effect, contributed to a better catalysis than the SnO₂ part.     

Cross‐hole resistivity tomography using different electrode configurations

This paper investigates the relative merits and effectiveness of cross‐hole resistivity tomography using different electrode configurations for four popular electrode arrays: pole–pole, pole–bipole, bipole–pole and bipole–bipole. By examination of two synthetic models (a dipping conductive strip and a dislocated fault), it is shown that besides the popular pole–pole array, some specified three‐ and four‐electrode configurations, such as pole–bipole AM–N, bipole–pole AM–B and bipole–bipole AM–BN with their multispacing cross‐hole profiling and scanning surveys, are useful for cross‐hole resistivity tomography. These configurations, compared with the pole–pole array, may reduce or eliminate the effect of remote electrodes (systematic error) and yield satisfactory images with 20% noise‐contaminated data. It is also shown that the configurations which have either both current electrodes or both potential electrodes in the same borehole, i.e. pole–bipole A–MN, bipole–pole AB–M and bipole–bipole AB–MN, have a singularity problem in data acquisition, namely low readings of the potential or potential difference in cross‐hole surveying, so that the data are easily obscured by background noise and yield images inferior to those from other configurations.     

Factors controlling the morphology and volume (V)–length (L) relations of permanent gullies in the northern Ethiopian Highlands

Small‐scale aerial photographs and high‐resolution satellite images, available for Ethiopia since the second half of the twentieth century as for most countries, allow only the length of gullies to be determined. Understanding the development of gully volumes therefore requires that empirical relations between gully volume (V) and length (L) are established in the field. So far, such V–L relations have been proposed for a limited number of gullies/environments and were especially developed for ephemeral gullies. In this study, V–L relations were established for permanent gullies in northern Ethiopia, having a total length of 152 km. In order to take the regional variability in environmental characteristics into account, factors that control gully cross‐sectional morphology were studied from 811 cross‐sections. This indicated that the lithology and the presence of check dams or low‐active channels were the most important controls of gully cross‐sectional shape and size. Cross‐sectional size could be fairly well predicted by their drainage area. The V–L relation for the complete dataset was V = 0 · 562 L ^1·381 (n = 33, r² = 0 · 94, with 34 · 9% of the network having check dams and/or being low‐active). Producing such relations for the different lithologies and percentages of the gully network having check dams and/or being low‐active allows historical gully development from historical remote sensing data to be assessed. In addition, gully volume was also related to its catchments area (A) and catchment slope gradient (S_c). This study demonstrates that V–L and V–A × S_c relations can be very suitable for planners to assess gully volume, but that the establishment of such relations is necessarily region‐specific. Copyright © 2013 John Wiley & Sons, Ltd.     

Sensitive Ion‐Flotation Separation of Ag(I) Traces Using 2‐(2‐Methoxyphenyl)benzimidazole before Flame Atomic Absorption Spectrometric Determination in Water

A sensitive, reliable, and environmentally friendly method for simple separation and preconcentration of Ag(I) traces in aqueous samples is presented prior to their flame atomic absorption spectrometric determinations. At pH 7.0, Ag(I) was separated with 2‐(2‐methoxyphenyl)benzimidazole (MPBI) as a new complexing agent and floated after adding sodium dodecyl sulfate (SDS) as a foaming reagent. The floated layer was then dissolved in proper amount of concentrated nitric acid in methanol and introduced to the flame atomic absorption spectrometer (FAAS). The effects of pH, concentration of MPBI, type and amount of surfactant as the floating agent, type and amount of eluting agent, and influence of foreign ions on the recovery of the analyte ion were investigated. Also, using a nonlinear curve fitting method, the formation constant of 1.62 × 10⁶ was obtained for Ag(I)–MPBI complex. The analytical curve was linear in the range of 1.8 × 10^?7–1.7 × 10^?6 mol/L for determination of Ag(I). The relative standard deviation (RSD; N = 10) corresponding to 0.7 × 10^?6 mol/L of Ag(I), the limit of detection (10 blanks), and the enrichment factor were obtained as 1.7%, 2.9 × 10^?8 mol/L, and 43.0, respectively. The proposed procedure was then applied successfully for determination of silver ions in different water samples.     

Application of a multi‐temporal,LiDAR‐derived,digital terrain model in a landslide‐volume estimation

Sediments produced by landslides are crucial in the sediment yield of a catchment, debris flow forecasting, and related hazard assessment. On a regional scale, however, it is difficult and time consuming to measure the volumes of such sediment. This paper uses a LiDAR‐derived digital terrain model (DTM) taken in 2005 and 2010 (at 2 m resolution) to accurately obtain landslide‐induced sediment volumes that resulted from a single catastrophic typhoon event in a heavily forested mountainous area of Taiwan. The landslides induced by Typhoon Morakot are mapped by comparison of 25 cm resolution aerial photographs taken before and after the typhoon in an 83.6 km² study area. Each landslide volume is calculated by subtraction of the 2005 DTM from the 2010 DTM, and the scaling relationship between landslide area and its volume are further regressed. The relationship between volume and area are also determined for all the disturbed areas (V_L = 0.452A_L^1.242) and for the crown areas of the landslides (V_L = 2.510A_L^1.206). The uncertainty in estimated volume caused by use of the LiDAR DTMs is discussed, and the error in absolute volume estimation for landslides with an area >10⁵ m² is within 20%. The volume–area relationship obtained in this study is also validated in 11 small to medium‐sized catchments located outside the study area, and there is good agreement between the calculation from DTMs and the regression formula. By comparison of debris volumes estimated in this study with previous work, it is found that a wider volume variation exists that is directly proportional to the landslide area, especially under a higher scaling exponent. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of Short‐term and Long‐term Aluminium Stress on Photosynthesis,Respiration, and Reproductive Capacity in a Unicellular Green Flagellate (Euglena gracilis)

Effects of short‐term (1 h exposure) and long‐term (7 d exposure) aluminium stress on photosynthesis and reproductive capacity have been studied in Euglena gracilis strain Z. Following concentrations of Al_tot (added as AlCl₃) were tested: 0.5 mg L^‐1, 1.0 mg L^‐1, 1.5 mg L^‐1, 2.5 mg L^‐1, 5.0 mg L^‐1, 7.5 mg L^‐1, 10.0 mg L^‐1, and 15.0 mg L^‐1 Al, respectively. Growth rates at different aluminium concentrations did not show significant differences, except at 15.0 mg L^‐1Al. Initial respiration was higher in long‐term than in the short‐term experiments. It is supposed that an energy‐dependent mechanism of excretion of aluminium ions has been active in the stressed cells. Consequently, the cells of E. gracilis after long‐term exposure to aluminium are believed to be more acclimatised to the aluminium stress. Photosynthetic efficiency (PE) has been negatively affected by aluminium in all experiments performed. Differences between control algae and those treated with aluminium were significant in all cases. PE in long‐term experiments was in general significantly higher at all concentrations of aluminium studied, compared to the short‐term experiments. The aluminium concentrations tested led only to a general decrease in PE while the level of decrease was not especially concentration‐dependent. In general, aluminium tolerance of E. gracilis can be estimated as low, especially by short‐term exposure. However, good acclimatisation capacity of this green flagellate to aluminium doses by long‐term exposure can be supposed.     

Occurrence of an Algal Mass Development in an Acidic (pH 2.5):, Iron and Aluminium‐rich Coal Mining Pond

A bloom of Chlamydomonas botryopara was observed in an extremely acid coal mining pond (pH 2.5) with high concentrations of iron and aluminium (1160...3760 mg L^–1 Fe, 133...387 mg L^–1 Al). Cell density of algae was counted as 6.45 · 10⁶ mL^–1 corresponding to 700 mg L^–1 fresh weight and 2660 μg L^–1 chlorophyll‐a. The nutrient concentrations were 3.5 mg L^–1 soluble reactive phosphorus and 0.15 mg L^–1 dissolved inorganic nitrogen. This observation supports the hypothesis that a low nutrient availability rather than extreme conditions (e.g. high acidity and low pH) limit the development of phytoplankton in many acidified lakes.     

Bioassay‐directed fractionation for analyzing estrogens in surface waters of the German Baltic Sea

A reversed‐phase fractionation method with subsequent biological and chemical analysis has been developed to estimate the contributions of the most potent estrogens to observed estrogenic effect potentials. Surface water samples were taken in the German Baltic Sea (Inner Wismar Bay and Darss Peninsula, sampling campaign July 2003) and were separated into seven individual fractions. Three fractions showed significant estrogenic activities and clear dose‐dependant responses were obtained in the yeast estrogen screen (YES). In the 2nd fractions liquid chromatographic‐electrospray‐tandem mass spectrometric (LC‐ESI‐MS‐MS) analyses showed the presence of bisphenol A (Inner Wismar Bay: 4.8 ng L^–1 and 6 ng L^–1; Darss Peninsula: 0.91 ng L^–1 and 1.7 ng L^–1) and ethinylestradiol (Inner Wismar Bay: 2.0 ng L^–1 and 6.0 ng L^–1; Darss Peninsula: < MDL and 1.7 ng L^–1), whereas estrogenic activities in the YES were only around 10% of the positive control E2. Although not identified prior in the total extract the natural hormones estradiol (Inner Wismar Bay: 0.13 ng L^–1 and 0.19 ng L^–1; Darss Peninsula: 0.12 ng L^–1 and 0.16 ng L^–1) and estriol (Inner Wismar Bay: < MDL and 0.33 ng L^–1; Darss Peninsula: < MDL) could be detected in the 3rd fractions, where high estrogenic potentials could be observed. The 4th fractions showed high responses as well and estrone were herein quantified with concentrations of 0.16 ng L^–1 and 0.18 ng L^–1 (Darss Peninsula) up to 0.37 ng L^–1 (Inner Wismar Bay). Measured and calculated estradiol equivalents for individual fractions correlated very well (R² = 0.78), when disregarding results of the 2nd fraction, where high deviations occurred.     

Simultaneous Analysis of Natural Free Estrogens and Their Conjugates in Wastewater by GC‐MS

A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L^–1, respectively. However, only E1 was detected at a high concentration of 44 ng L^–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.     

Zur Konzentrationsabhängigkeit der Sorption von Co(II) an Titanschwamm

The sorption of Co(II) from aqueous solutions on granulated titanium dioxide was investigated in dependence on pH-value (pH = 6 … 10) and solution concentration (c_L = 10^?7 … 10^?2 mol/kg) at 83 °C. The precipitation in the solution occurred at high pH-values and solution concentrations was determined by control experiments without the adsorber. The adsorption isotherms are S-shaped. This can be interpreted as transition from chemisorption at the basic material to surface precipitation.     

Optimal Field Approaches for Electrokinetic In Situ Oxidation Remediation

Numerical simulations were used to identify and evaluate optimum electrode configurations and approaches for electrokinetic in situ chemical oxidation (EK‐ISCO) remediation of low‐permeability sediments. A newly developed groundwater and EK flow and reactive transport numerical model was used to conduct two‐dimensional scenario simulations of the coverage of an injected oxidant, permanganate, and the oxidation of a typical organic contaminant (tetrachloroethene, PCE). For linear configurations of vertical electrodes, the spacing of same‐polarity electrodes is recommended to be about one‐third to one‐quarter of the anode–cathode spacing. Greater coverage could also be achieved by locating additional oxidant injection wells at the divergence of the electric field in linear electrode configurations. Horizontal electrodes allowed greater contact between the injected permanganate and PCE and resulted in faster degradation of PCE compared to vertical electrodes. Pulsed oxidant injection, closer electrode spacing, and electric field reversal also resulted in faster EK‐ISCO remediation.     

Kinetics,Mechanistic and Thermodynamics of Zn(II) Ion Sorption: A Modeling Approach

Biosorption potential of Cedrus deodara sawdust (CDS) in terms of sorption of Zn(II) ion across liquid phase has been evaluated in the present investigation. The surface of the CDS biomass before the sorption of Zn(II) ions seemed to be more porous, non‐crystalline and heterogeneous. The maximum uptake capacity of CDS was 97.39 mg g^?1. Sorption of Zn(II) ion on the surface of CDS sawdust was maximum at pH 5, temperature 45°C, initial concentration of Zn(II) ion 100 mg L^?1, biomass dose 1 g L^?1, contact time 150 min, and agitation rate 160 rpm. Pseudo second‐order kinetics with the highest linear regression coefficient (R² = 0.99), and lowest values of error functions, i.e., chi (χ²) and sum of square errors (SSE) against pseudo first‐order rate kinetics showed that the sorption of Zn(II) ion on the surface of CDS was mediated by chemosoprtive forces of attraction rather than physical adsorption. Mechanistically, relatively higher proportion of sorption of Zn(II) ion in early phase of contact time was profoundly explained by Bangham's equation and film diffusivity (D^f). Intraparticle or pore diffusion (D_p) of Zn(II) ion inside the pores of CDS was rate limiting step at the later stage of contact time. Furthermore, the thermodynamic study on sorption of metal ion delineated the fact that the Zn(II) sorption on the surface of CDS was spontaneous, endothermic together with increased entropy at solid liquid interface.     

Wetland nitrogen dynamics in an Adirondack forested watershed

Wetlands often form the transition zone between upland soils and watershed streams, however, stream–wetland interactions and hydrobiogeochemical processes are poorly understood. We measured changes in stream nitrogen (N) through one riparian wetland and one beaver meadow in the Archer Creek watershed in the Adirondack Mountains of New York State, USA from 1 March to 31 July 1996. In the riparian wetland we also measured changes in groundwater N. Groundwater N changed significantly from tension lysimeters at the edge of the peatland to piezometer nests within the peatland. Mean N concentrations at the peatland perimeter were 1·5, 0·5 and 18·6 µmol L^?1 for NH₄⁺, NO₃^? and DON (dissolved organic nitrogen), respectively, whereas peatland groundwater N concentration was 56·9, 1·5 and 31·6 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively. The mean concentrations of stream water N species at the inlet to the wetlands were 1·5, 10·1 and 16·9 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively and 1·6, 28·1 and 8·4 µmol L^?1 at the wetland outlet. Although groundwater total dissolved N (TDN) concentrations changed more than stream water TDN through the wetlands, hydrological cross‐sections for the peatland showed that wetland groundwater contributed minimally to stream flow during the study period. Therefore, surface water N chemistry was affected more by in‐stream N transformations than by groundwater N transformations because the in‐stream changes, although small, affected a much greater volume of water. Stream water N input–output budgets indicated that the riparian peatland retained 0·16 mol N ha^?1 day^?1 of total dissolved N and the beaver meadow retained 0·26 mol N ha^?1 day^?1 during the study period. Nitrate dominated surface water TDN flux from the wetlands during the spring whereas DON dominated during the summer. This study demonstrates that although groundwater N changed significantly in the riparian peatland, those changes were not reflected in the stream. Consequently, although in‐stream changes of N concentrations were less marked than those in groundwater, they had a greater effect on stream water chemistry—because wetland groundwater contributed minimally to stream flow. Copyright © 2004 John Wiley & Sons, Ltd.     

Characterization of rocking shallow foundations using centrifuge model tests

This paper presents new results of centrifuge model tests exploring the behavior of rocking shallow foundations embedded in dry sand, which provides a variety of factors of safety for vertical bearing. The results of slow (quasi‐static) cyclic tests of rocking shear walls and dynamic shaking tests of single‐column rocking bridge models are presented. The moment–rotation and settlement–rotation relationships of rocking footings are investigated. Concrete pads were placed in the ground soil to support some models with the objective of reducing the settlement induced by rocking. The behavior of rocking foundation was shown to be sensitive to the geometric factor of safety with respect to bearing failure, L_f/L_c, where L_f was the footing length, and the L_c was the critical soil‐footing contact length that would be required to support pure axial loading. Settlements were shown to be small if L_f/L_c was reasonably large. Placement of concrete pads under the edges of the footing was shown to be a promising approach to reduce settlements resulting from rocking, if settlements were deemed to be excessive and also had impacts on the energy dissipation and rocking moment capacity. A general discussion of the tradeoffs between energy dissipation and re‐centering of rocking foundations and other devices is included. Copyright © 2011 John Wiley & Sons, Ltd.