Photodegradation,Photocatalytic, and Aerobic Biodegradation of Sulfisomidine and Identification of Transformation Products by LC–UV‐MS/MS

Much attention has recently been devoted to the fate and effects of pharmaceuticals in the water cycle. Removal of antibiotics in effluents by photo‐treatment or biodegradation is a topic currently under discussion. Degradation and removal efficiencies of sulfisomidine (SUI) by photodegradation and aerobic biodegradability were studied. SUI behavior was monitored during photolysis and photocatalysis (catalyst titanium dioxide) using 150‐W medium‐pressure Hg lamp. Also an aerobic bacterial degradation test from the OECD series (closed bottle test (CBT, OECD 301 D)) was performed. The primary elimination of SUI was monitored. Structures of photo‐degradation products were assessed by chromatographic separation on a C18 column with ultraviolet detection at 270 nm and ion trap MS. The results demonstrate that SUI is not readily biodegradable in CBT. Photo catalysis was more is effective than photolysis. SUI underwent photodegradation and several SUI photoproducts were identified. Accordingly, the photodegradation pathway of SUI was postulated. When reaching the aquatic environment, SUI and its photo products can constitute a risk to the environment.     

Chute channel dynamics in large,sand‐bed meandering rivers

Meander bends of many large, sand‐bed meandering rivers are partitioned by chute channels that convey permanent flow, and co‐exist with the mainstem for decades. As a first step toward understanding the dynamics and morphodynamic implications of these ‘bifurcate meander bends’, this study applied binary logistic regression analysis to determine whether it is possible to predict chute initiation based on attributes of meander bend character and dynamics. Regression models developed for the Strickland River, Papua New Guinea, the lower Paraguay River, Paraguay/Argentina, and the Beni River, Bolivia, revealed that the probability of chute initiation at a meander bend is a function of the bend extension rate (the rate at which a bend elongates in a direction perpendicular to the valley axis trend). Image analyses of all rivers and field observations from the Strickland suggest that the majority of chute channels form during scroll–slough development. Rapid extension is shown to favour chute initiation by breaking the continuity of point bar deposition and vegetation encroachment at the inner bank, resulting in widely‐spaced scrolls with intervening sloughs that are positively aligned with primary over‐bar flow. The rivers plot in order of increasing chute activity on an empirical meandering‐braided pattern continuum defined by potential specific stream power (ω_pv) and bedload calibre (D₅₀). Increasing stream power is considered to result in higher bend extension rates, with implications for chute initiation. In addition, chute stability is shown to depend on river sediment load relative to flow discharge (Qs/Q), such that while the Beni may plot in the region of highly braided rivers by virtue of a high potential specific stream power, the formation of stable chute channels is suppressed by the high sediment load. This tendency is consistent with previous experimental studies, and results in a planform that is transitional between single‐thread meandering and braided. Copyright © 2011 John Wiley & Sons, Ltd.     

Interaction between meander dynamics and floodplain heterogeneity in a large tropical sand‐bed river: the Rio Beni,Bolivian Amazon

The evolution of meandering river floodplains is predominantly controlled by the interplay between overbank sedimentation and channel migration. The resulting spatial heterogeneity in floodplain deposits leads to variability in bank erodibility, which in turn influences channel migration and planform development. Despite the potential significance of these feedbacks, few studies have quantified their impact upon channel evolution and floodplain construction in dynamic settings (e.g. locations characterized by rapid channel migration and high rates of overbank sedimentation). This study employs a combination of field observations, geographic information system (GIS) analysis of satellite imagery and numerical modelling to investigate these issues along a 375 km reach of the Rio Beni in the Bolivian Amazon. Results demonstrate that the occurrence of clay‐rich floodplain deposits promotes a significant reduction in channel migration rates and distinctive styles of channel evolution, including channel straightening and immobilization of bend apices leading to channel narrowing. Clay bodies act as stable locations limiting the propagation of planform disturbances in both upstream and downstream directions, and operate as ‘hinge’ points, around which the channel migrates. Spatial variations in the erodibility of clay‐rich floodplain material also promote large‐scale (10–50 km) differences in channel sinuosity and migration, although these variables are also likely to be influenced by channel gradient and tectonic effects that are difficult to quantify. Numerical model results suggest that spatial heterogeneity in bank erodibility, driven by variable bank composition, may force a substantial (c. 30%) reduction in average channel sinuosity, compared to situations in which bank strength is spatially homogeneous. Copyright © 2015 John Wiley & Sons, Ltd.     

Algal-silica cycling and pigment diagenesis in recent alpine lake sediments: mechanisms and paleoecological implications

The quality and interpretability of the paleobiological record depends on the preservation of morphological and geochemical fossils. Siliceous microfossils and sedimentary pigments are often cornerstones in paleoecology, although the microbial and geochemical processes conducive to their preservation remain poorly constrained. We examined sediments from an alpine lake in Banff National Park (Alberta, Canada) where diatom frustules are completely dissolved within 50 years of deposition. Diatom dissolution, silica recycling, and diagenetic alteration of algal pigments were investigated, in conjunction with porewater geochemistry and microelectrode profiling of the sediment–water interface. Analysis of sediment trap material showed ~90% of biogenic silica (BSi) production is lost prior to burial. Silica flux calculations, based on dissolved silica (as H₄SiO₄) in pore-waters, show a further ~6% of total BSi is returned to the water column from the upper 4 cm of sediments, implying that only ~4% of total BSi is permanently archived in sediments. In situ sediment pH and O₂ profiles reveal that aerobic respiration by bacteria fully consumes oxygen by a depth of 4 mm into the sediment, with associated strong pH and redox gradients. During sedimentation and early diagenesis, diatoms undergo loss of extracellular polymeric substances that coat their frustules, promoting silica dissolution and leading to the loss of the microfossil record by a depth of 3.25 cm. Sedimentary pigments similarly undergo rapid degradation, but diatom-related carotenoids persist below the depth of silica dissolution. This work provides new insights on diagenetic processes in lakes, with broad implications for the interpretation of sedimentary proxies for algal production.     

Determination of the freshwater budget of tidal flats from measurements near a tidal inlet

The freshwater budget of a tidal flat area is evaluated from long-term hydrographic time series from an observation pole positioned in a tidal channel in the Hörnum Basin (Germany). For each tidal cycle, the freshwater budget is calculated from the total imported and exported water volumes and the corresponding mean densities. The variability of the budget on a tidal scale is characterised by a period of twice the tidal period, exhibiting a minimum when the tidal flats are dry around daylight hours during the foregoing low tide, and a maximum when low tide occurs at night; enhanced evaporation on the flats at daylight hours is identified as the driving process. On the average over one year, while winter observations are missing, the freshwater budget is negative for the years 2002–2005 and positive only for 2006. The interannual mean is negative and amounts to a freshwater loss of about 2 mm day⁻¹, although the large-scale climate in this region is humid. The results demonstrate that the bulk parametrisations for the latent and sensible heat flux between the ocean and the atmosphere must not be applied for the tidelands.     

Pyritization of Iron in Sediments from the Continental Slope of the Northern Gulf of Mexico

In sediments from the continental slope of the Northern Gulf of Mexico, generally,the degree of iron pyritization (DOP) is low (<0.1) and dissolved sulfide is belowdetection limits (5 M), whereas dissolved Fe is typically about 50 to100 M. Therefore, the dissolution of kinetically reactive iron minerals generallydominates over the rate of sulfide production in sediments throughout this region.However, in sediments where hydrocarbons have been added via seepage from thesubsurface, dissolved-Fe is undetectable, DOP can approach 1, and high concentrationsof dissolved sulfide (up to 11 mM) are commonly present. Even though thesesediments have high total reduced sulfide (TRS) concentrations (typically 150 to370 mol gdw^-1), their average C/S ratio is about 4 times that of normal marine sediments reflecting the major input of hydrocarbons. DOP is significantly (20%) higher when calculated using reactive-Fe extracted by citrate dithionite than by cold 1N HCl. This difference is primarily due to the greater extraction efficiency of the cold HCl method for silicate-Fe. TRS tends to rise to a maximum, and remains close to constant even at high (mM) dissolved sulfide concentrations. These TRS concentrations, therefore, represent the size of the ``kinetically' reactive-Fe pool during early diagenesis.     

Tracing element sources of hydrothermal mineral deposits: REE and Y distribution and Sr-Nd-Pb isotopes in fluorite from MVT deposits in the Pennine Orefield,England

Fluorite from Mississippi Valley Type (MVT) deposits in the South Pennine Orefield, England, displays significantly different distributions of rare earths and yttrium (REY) compared to fluorite from similar MVT deposits in the North Pennine Orefield. Samples from the South Pennine Orefield display negative Ce and positive Gd and Y anomalies but lack any Eu anomaly, indicating that the REY were mobilized from relatively pure marine sedimentary carbonates. In marked contrast, fluorite from the North Pennine Orefield lacks any Ce and Gd anomalies but shows a pronounced positive Eu anomaly, suggesting that the REY were provided by different source rock(s), that the mineralizing hydrothermal fluid had experienced higher temperatures prior to fluorite precipitation, and that it was derived from deeper crustal levels in the north compared to the south. The isotopic composition of Sr in Blue John fluorite from the South Pennine Orefield suggests that Sr was mobilized from Lower Carboniferous (Tournaisian) limestones, whereas Pb isotopes suggest that in contrast to REY and Sr, Pb was derived from aluminosilicate rocks. Neither Nd nor Sr or Pb isotopes can be used to radiometrically date the formation of Blue John fluorite. All isotope systems studied indicate that the limestone host rock of this fluorite mineralization did not contribute to the trace element budget of the hydrothermal fluid. Our results show that different solutes in a natural water (hydrothermal fluid, groundwater, etc.) may be derived from different sources, and that the study of a small set of elements or isotope ratios may not provide full insight into the genesis or history of a mineralization or a hydrothermal fluid. Our data provide evidence for the uncoupling of Sr, Nd and Pb during fluid-rock interaction and fluid migration, and show that the use of plots such as ⁸⁷Sr/⁸⁶Sr vs. _Nd. to learn about mixing relationships (as is commonly done in igneous geochemistry) is unreliable when applied to natural waters and their precipitates.Editorial handling: B. Lehmann     

Initial Pb–Sr(–Nd) isotopic heterogeneity in a single allanite–epidote crystal: implications of reaction history for the dating of minerals with low parent-to-daughter ratios

We analyzed 17 fragments from a zoned allanite–epidote crystal (ca 2.2 mm × 4.0 mm), which had formed during different prograde and retrograde stages of ultra high pressure (UHP) and amphibolite facies metamorphism (240–230 Ma, Sulu Belt, E China), for the isotopic composition of Pb, Nd, and Sr and contents of Pb, U, and Th, Sr and Rb, and Nd and Sm. Since most fragments had ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb values less than 1, corrections for in situ Pb growth are small and uncertainties in the recalculation of the Pb isotopic compositions to 240 Ma are insignificant. The recalculated Pb falls on a linear trend in the ²⁰⁶Pb/²⁰⁴Pb vs ²⁰⁷Pb/²⁰⁴Pb diagram with the allanite defining the low–²⁰⁶Pb/²⁰⁴Pb end (17.07) of this trend and the epidote defining its high–²⁰⁶Pb/²⁰⁴Pb end (17.56). The recalculated data scatter in the ²⁰⁶Pb/²⁰⁴Pb vs ²⁰⁸Pb/²⁰⁴Pb diagram, which implies that the initial Pb isotopic variation reflects the involvement of at least three different Pb sources. The low ⁸⁷Rb/⁸⁶Sr values account for a change in ⁸⁷Sr/⁸⁶Sr by in situ ⁸⁷Sr growth of less than 0.0007, which implies that the isotopic heterogeneity of ⁸⁷Sr/⁸⁶Sr (0.70601–0.7200) is a primary feature. The Pb and Sr isotope data unequivocally demonstrate that contributions from different precursor minerals result in initial isotopic heterogeneity in the metamorphic reaction product. It is likely that such an initial isotopic heterogeneity also exists for Nd, but it could not be resolved in the present study. Initially heterogeneous Pb and Sr isotope compositions imply that age differences between core and rim of large crystals may result in the determination of highly arbitrary geological rates, especially for minerals with relatively low parent-to-daughter ratios.     

Eddy Covariance Measurements On Mountain Slopes: The Advantage Of Surface-Normal Sensor Orientation Over A Vertical Set-Up

The measurement of scalar fluxes employing the eddy covariance method is a widely used experimental approach,for which the flow distortion due to obstacles (e.g., sensor mounts and mast)is a well-known but not fully solved problem. In order to reduce flow distortion we installed a sonic anemometer in a surface-normal orientationrelative to the terrain slope, and a second instrument in a verticalposition at a horizontal distance of 1.54 m from the first instrumentWe found a significant reduction in the rotation angle necessary for the coordinaterotation procedure in the x-z plane whencomputing 30-minute flux averages with the surface-normal orientation. In 91% of all cases this rotation angleremained within the angle of incidence of ±10° recommended bythe manufacturer. In contrast, only 24% of the measurements taken with the vertically mounted anemometer were obtained at an angle of incidencewithin ±10°, and 3% were outside the ±30° range specified for an acceptable operation.A data quality test based on the variance of vertical windspeed normalized with friction velocity (_w/u_*) revealed problems for application under stable conditions due to large uncertainties in the determination of the Monin–Obukhov stability parameter z/L. An alternative test using the bulk drag coefficient C_D revealed other problems related to the dependence of C_D on z/z₀, the measuring height normalized by the roughness length, which do not appear to be constantin complex terrain. With both tests, a tendency for a slightly improved dataquality was found for the surface normal set-up, which, however, proved statistically insignificant.It is concluded that the surface-normal set-up of a sonic anemometer significantly reduces flow distortion by thesensor head. Although the surface-normal mounting position therefore appears to be the preferred one, with decreased flow distortion and a slightly improved data quality, no significant differences in turbulent quantities were found between the two set-uppositions. Hence, the consequences for short-term measurements of massand energy fluxes with a surface-normal set-up in complex terrain appearto be relevant only if single flux events are to be inspected, while for long-term measurements of integrated fluxes both the surface-normaland vertical installation of the sonic anemometer are adequate,indicating that eddy covariance measurements in complex terrain are lessdelicate than expected.     

Pitch-angle distributions in and near the loss cone of (100–350) keV protons

The pitch-angle distributions in and near the loss cone, of ～ (100–200) and ～ (200–350) keV protons observed by the ESRO IB satellite during the period 7–15 October 1969 are presented. The data include periods of relative quiet as well as more disturbed geomagnetic conditions. Spatial characteristics and dynamics of the protons, both on the night-and dayside of the Earth are described. The actual pitch-angle distribution is interpreted as produced by wave-particle interactions, and the diffusion coefficient and lifetime against pitch angle scattering have been estimated from existing theories. During slightly disturbed conditions, the observations suggest an average random walk in pitch angle made by a particle during a crossing of the diffusion region of about one half of the loss cone half angle for 4 ? L ? 6. The lifetime against pitch angle scattering into the loss cone is found to be somewhat less than the charge exchange lifetime for these (100–350) keV protons. The spectral density of interacting waves is tentatively estimated to about 0·1 $\text{γ}{}^2\text{Hz}$, and compares with estimates arrived at from completely different approaches.