Adsorption of BTEX on Surfactant Modified Granulated Natural Zeolite Nanoparticles: Parameters Optimizing by Applying Taguchi Experimental Design Method

In this paper, a novel adsorbent developed by means of granulating of natural zeolite nanoparticles (i.e., clinoptilolite) was evaluated for possible removal of the petroleum monoaromatics (i.e., benzene, toluene, ethylbenzene, and xylene, BTEX). To do this, the natural zeolite was ground to produce nanosized particulate, then modified by two cationic surfactants and granulated. The effect of various parameters including temperature, initial pH of the solution, total dissolved solids (TDS), and concentration of a competitive substance (i.e., methyl tert‐butyl ether, MTBE) were studied and optimized using a Taguchi statistical approach. The results ascertained that initial pH of the solution was the most effective parameter. However, the low pH (acidic) was favorable for BTEX adsorption onto the developed adsorbents. In this study, the experimental parameters were optimized and the best adsorption condition by determination of effective factors was chosen. Based on the S/N ratio, the optimized conditions for BTEX removal were temperature of 40°C, initial pH of 3, TDS of 0 mg/L, and MTBE concentration of 100 µg/L. At the optimized conditions, the uptake of each BTEX compounds reached to more than 1.5 mg/g of adsorbents.     

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.     

Temperature in lowland Danish streams: contemporary patterns,empirical models and future scenarios

Continuous temperature measurements at 11 stream sites in small lowland streams of North Zealand, Denmark over a year showed much higher summer temperatures and lower winter temperatures along the course of the stream with artificial lakes than in the stream without lakes. The influence of lakes was even more prominent in the comparisons of colder lake inlets and warmer outlets and led to the decline of cold‐water and oxygen‐demanding brown trout. Seasonal and daily temperature variations were, as anticipated, dampened by forest cover, groundwater input, input from sewage plants and high downstream discharges. Seasonal variations in daily water temperature could be predicted with high accuracy at all sites by a linear air‐water regression model (r²: 0·903–0·947). The predictions improved in all instances (r²: 0·927–0·964) by a non‐linear logistic regression according to which water temperatures do not fall below freezing and they increase less steeply than air temperatures at high temperatures because of enhanced heat loss from the stream by evaporation and back radiation. The predictions improved slightly (r²: 0·933–0·969) by a multiple regression model which, in addition to air temperature as the main predictor, included solar radiation at un‐shaded sites, relative humidity, precipitation and discharge. Application of the non‐linear logistic model for a warming scenario of 4–5 °C higher air temperatures in Denmark in 2070‐2100 yielded predictions of temperatures rising 1·6–3·0 °C during winter and summer and 4·4–6·0 °C during spring in un‐shaded streams with low groundwater input. Groundwater‐fed springs are expected to follow the increase of mean air temperatures for the region. Great caution should be exercised in these temperature projections because global and regional climate scenarios remain open to discussion. Copyright © 2006 John Wiley & Sons, Ltd.     

The Carbonate Radical (HCO3·/CO3–·) as a Reactive Intermediate in Water Chemistry: Kinetics and Modelling

Results from kinetic laboratory studies of reactions of the carbonate radical anion (CO₃^–·) with aromatic compounds in aqueous solution at T = 298 K are presented. Data were obtained in using a laser photolysis laser long-path absorption (LP-LPLA) apparatus which was designed for direct time-resolved studies of radical reactions. For the reactions of CO₃^–· with hydroquinone dimethyl ether (2), methyl anisole (3), benzene (4), p-xylene (5), toluene (6), chlorobenzene (7), nitrobenzene (8), and benzonitrile (9), rate coefficients of k₂ = (3.0 ± 0.6)·10⁷ M^–1 s^–1, k₃ = (9.7 ± 1.7)·10⁵ M^–1 s^–1, k₄ = (3.2 ± 0.7)·10⁵ M^–1 s^–1, k₅ = (3.8 ± 0.9)·10⁴ M^–1 s^–1, k₆ = (6.8 ± 2.3)·10⁴ M^–1 s^–1, k₇ = (2.7 ± 0.6)·10⁵ M^–1 s^–1, k₈ = (1.4 ± 0.5)·10⁴ M^–1 s^–1, and k₉ < 1.3·10² M^–1 s^–1 were obtained. In further studies the effect of temperature on the reactions (2), (4), and (5) has been studied. The kinetic data obtained for the reaction of the carbonate radical anion with aromatic compounds were compared to the corresponding reactions of the hydroxyl radical. Finally, these kinetic data were used within a simple model system to investigate the implications of carbonate radical anion kinetics within water treatment processes. It is shown that the degradation of organic pollutants in ^·OH-radical based water treatment may proceed via the CO₃^–·/HCO_3· radical under certain conditions.     

Hydrological processes controlling ground and surface water flow from a hypermaritime forest–peatland complex,Diana Lake Provincial Park,British Columbia,Canada

The proposed harvesting of previously undeveloped forests in north coastal British Columbia requires an understanding of hydrological responses. Hydrometric and isotopic techniques were used to examine the hydrological linkages between meteoric inputs to the surface‐groundwater system and runoff response patterns of a forest‐peatland complex. Quickflow accounted for 72–91% of peak storm discharge. The runoff ratio was lowest for open peatland areas with thick organic horizons (0·02–0·05) due to low topographic gradients and many surface depressions capable of retaining surface water. Runoff ratio increased comparatively for ephemeral surface seep flows (0·06–0·40) and was greatest in steeply sloping forest communities with more permeable soils (0·33–0·69). The dominant mechanism for runoff generation was saturated shallow subsurface flow. Groundwater fluxes from the organic horizon of seeps (1·70–1·72 m³ day^?1 m^?1) were an important component of quickflow. The homogeneous δ²H? δ¹⁸O composition of groundwater indicated attenuation of the seasonal rainfall signal by mixing during recharge. The positive correlation (r² = 0·64 and 0·38, α = 0·05) between slope index and δ¹⁸O values in groundwater suggests that the spatial pattern in the δ¹⁸O composition along the forest‐peatland complex is influenced by topography and provides evidence that topographic indices may be used to predict groundwater residence time. Copyright © 2006 John Wiley & Sons, Ltd.     

Long term remeasurements of micro-erosion meter rates,Aldabra Atoll,Indian Ocean

Micro-erosion meter sites, installed on Aldabra Atoll, Indian Ocean in 1969 to measure erosion rates in coastal and subaerial sites, were remeasured in 1971 and again in 1982. The orders of magnitude of calculated erosion rates are comparable but the precise figures and patterns differ. For subaerial sites the short term (1969–71) range of 0·11–0·58 mm a^?1 compares with a long term (1971–82) range of 0·06–0·75 mm a^?1; for coastal sites short term ranges of 0·002–7·5 mm a^?1 compare with long term rates of 0·09–2·7 mm a^?1. Interpretation and extrapolation of short term data should only be made with caution.     

Oxygen isotopic composition of low-temperature authigenic clinoptilolite

Oxygen isotope ratios were obtained from authigenic clinoptilolites from Barbados Accretionary Complex, Yamato Basin, and Exmouth Plateau sediments (ODP Sites 672, 797, and 762) in order to investigate the isotopic fractionation between clinoptilolite and pore water at early diagenetic stages and low temperatures. Dehydrated clinoptilolites display isotopic ratios for the zeolite framework (δ¹⁸O_f) that extend from +18.7‰ to +32.8‰ (vs. SMOW). In combination with associated pore water isotope data, the oxygen isotopic fractionation between clinoptilolite and pore fluids could be assessed in the temperature range from 25°C to 40°C. The resulting fractionation factors of 1.032 at 25°C and 1.027 at 40°C are in good agreement with the theoretically determined oxygen isotope fractionation between clinoptilolite and water. Calculations of isotopic temperatures illustrate that clinoptilolite formation occurred at relatively low temperatures of 17°C to 29°C in Barbados Ridge sediments and at 33°C to 62°C in the Yamato Basin. These data support a low-temperature origin of clinoptilolite and contradict the assumption that elevated temperatures are the main controlling factor for authigenic clinoptilolite formation. Increasing clinoptilolite δ¹⁸O_f values with depth indicate that clinoptilolites which are now in the deeper parts of the zeolite-bearing intervals had either formed at lower temperatures (17–20°C) or under closed system conditions.     

Factors controlling stable oxygen,hydrogen and carbon isotope ratios in regional groundwater of the eastern United Arab Emirates (UAE)

Increasing groundwater salinity and depletion of the aquifers are major concerns in the UAE. Isotopes of oxygen, hydrogen, and carbon concentrations in groundwater were used to estimate evaporation loss using the isotopes of oxygen and hydrogen, and using a carbon isotope to trace inorganic carbon cycling in two main aquifers in the eastern part of the United Arab Emirates. The δD‐δ¹⁸O of groundwater samples plotted on a line given by: δD = 4 δ¹⁸O + 4 ·4 (r² = 0·4). In comparison, the local meteoric water line (LMWL) has been defined by the line: δD = 8 δ¹⁸O + 15. In order to better understand the system investigated, samples were separated into two groups based on the δD‐δ¹⁸O relationship. These are (1) samples that plot above the LMWL (δD = 6·1 δ¹⁸O + 12·4, r² = 0·8) and which are located predominantly in the north of the study area, and (2) samples that plot below the LMWL (δD = 5·6 δ¹⁸O + 6·2, r² = 0·8) and which are mostly distributed in the south. Slopes for both the groups are similar and lower than that for LMWL indicating potential evaporation of recharging water. However, the y‐intercept, which differs between the two groups, suggests evaporation of return flow and evapotranspiration in the unsaturated zone to be more significant in the south. This is attributed to intense agricultural activities in the region. Samples from the eastern Gravel Plain aquifer have δ¹³C and dissolved inorganic carbon (DIC) values in the range from ? 10 to 17‰, and 12–100 mg C/l, respectively, while the range for those from the Ophiolite aquifer is from ? 11 to ? 16.4‰, and 16–114 mg C/l respectively. This suggests the control of C‐3 and C‐4 plants on DIC formation, an observation supported by the range δ¹³C of soil organic matter (from ? 18·5 to ? 22·1‰.) Copyright © 2007 John Wiley & Sons, Ltd.     

Stable isotope tracers as diagnostic tools in upscaling flow path understanding and residence time estimates in a mountainous mesoscale catchment

δ¹⁸O measurements of precipitation and stream waters were used as a natural tracer to investigate hydrological pathways and residence times in the River Feshie, a complex mesoscale (231 km²) catchment in the Cairngorm Mountains of Scotland. Precipitation δ¹⁸O exhibited strong seasonal variation over the 2001–02 hydrological year, ranging from −6·9‰ in the summer, to −12·0‰ during winter snowfalls (mean δ¹⁸O −9·59‰). Although damped, this seasonality was reflected in stream water outputs at seven sampling sites in the catchment, allowing δ¹⁸O variations to be used to infer hydrological source areas. Thus, stream water δ¹⁸O was generally controlled by a seasonally variable storm flow end member, mixing with groundwater of more constant isotopic composition. Periodic regression analysis allowed the differences in this mixing process between monitoring subcatchments to be assessed more quantitatively to provide a preliminary estimate of mean stream water residence time. This demonstrated the importance of responsive hydrological pathways associated with peat and shallow alpine soils in the headwater subcatchments in producing seasonally variable runoff with short mean residence times (33–113 days). In contrast, other tributaries with more freely draining soils and larger groundwater storage in shallow aquifers provided more effective mixing of variable precipitation inputs, resulting in longer residence time estimates (178–445 days). The mean residence time of runoff leaving the Feshie catchment reflected an integration of these contrasting influences (110–200 days). These insights from δ¹⁸O measurements extend the hydrological understanding of the Feshie catchment gained from other hydrochemical tracers, and demonstrate the utility of isotope tracers in investigating hydrological processes at the mesoscale. Copyright © 2005 John Wiley & Sons, Ltd.     

Geochemistry of meteoric diagenesis in carbonate islands of the northern Bahamas: 2. Geochemical modelling and budgeting of diagenesis

Geochemical characterization and numerical modelling of surface water and ground water, combined with hydrological observations, provide quantitative estimates of meteoric diagenesis in Pleistocene carbonates of the northern Bahamas. Meteoric waters equilibrate with aragonite, but water‐ rather than mineral‐controlled reactions dominate. Dissolutional lowering of the undifferentiated bedrock surface is an order of magnitude slower than that within soil‐filled topographic hollows, generating small‐scale relief at a rate of 65–140 mm ka^?1 and a distinctive pocketed topography. Oxidation of organic matter within the subsoil and vadose zones generates an average P of 4·0 × 10^?3 atm, which drives dissolution during vadose percolation and/or at the water table. However, these dissolution processes together account for <60% of the average rock‐derived calcium in groundwaters pumped from the freshwater lens. The additional calcium may derive from oxidation of organic carbon within the lens, accounting for the high P of the lens waters. Mixing between meteoric waters of differing chemistry is diagenetically insignificant, but evapotranspiration from the shallow water table is an important drive for subsurface cementation. Porosity generation in the shallow vadose zone averages 1·6–3·2% ka^?1. Phreatic meteoric diagenesis is focused near the water table, where dissolution generates porosity at 1·4–2·8% ka^?1. Maximum dissolution rates, however, are similar to those of evaporation‐driven precipitation, which occludes porosity of 4·0 ± 0·6% ka^?1. This drives porosity inversion, from primary interparticle to secondary mouldic, vug and channel porosity. In the deeper freshwater lens, oxidation of residual organic carbon and reoxidation of reduced sulphur species from deeper anaerobic oxidation of organic carbon may generate porosity up to 0·06% ka^?1. Meteoric diagenesis relies critically on hydrological routing and vadose thickness (controlled by sea level), as well as the geochemical processes active. A thin vadose zone permits direct evaporation from the water table and drives precipitation of meteoric phreatic cements even where mineral stabilization is complete. Copyright © 2007 John Wiley & Sons, Ltd.     

EXPORTS OF ORGANIC CARBON IN BRITISH RIVERS

This study provides the first detailed estimate of riverine organic carbon fluxes in British rivers, as well as highlighting major gaps in organic carbon data in national archives. Existing data on organic carbon and suspended solids concentrations collected between 1989 and 1993, during routine monitoring by the River Purification Boards (RPBs) in Scotland and the National River Authorities (NRAs) in England and Wales, were used with annual mean flows to estimate fluxes of dissolved and particulate organic carbon (DOC and POC) in British rivers. Riverine DOC exports during 1993 varied from 7·7–103·5 kg ha⁻¹ year⁻¹, with a median flux of 31·9 kg ha⁻¹ year⁻¹ in the 85 rivers for which data were available. There was a trend for DOC fluxes to increase from the south and east to the north and west. A predictive model based on mean soil carbon storage in 17 catchments, together with regional precipitation totals, explained 94% of the variation in the riverine DOC exports in 1993. This model was used to predict riverine DOC fluxes in regions where no organic carbon data were available. Calculated and predicted fluxes were combined to produce an estimate for exports of DOC to tidal waters in British rivers during 1993 of 0·68±0·07 Mt. Of this total, rivers in Scotland accounted for 53%, England 38% and Wales 9%. Scottish blanket peats would appear to be the largest single source of DOC exports in British rivers. An additional 0·20 Mt of organic carbon were estimated to have been exported in particulate form in 1993, approximately two–thirds of which was contributed by English rivers. It is suggested that riverine losses of organic carbon have the potential to affect the long-term dynamics of terrestrial organic carbon pools in Britain and that rivers may regulate increases in soil carbon pools brought about by climate change. © 1997 by John Wiley & Sons, Ltd.     

Quantification of TCE Co‐Oxidation in Groundwater Using a 14C–Assay

Bacteria that degrade natural organic matter in groundwater contain oxygenase enzymes that can co‐oxidize trichloroethene (TCE). This degradation pathway is promising for large dilute plumes, but its evaluation is limited because the density of the bacteria with oxygenase enzymes has not been correlated to field scale rates of degradation. A ¹⁴C–TCE assay was developed to determine pseudo first‐order rate constants for the aerobic co‐oxidation of TCE in groundwater. The assay involved incubating ¹⁴C–TCE in samples of groundwater contained in 160 mL serum bottles, and monitoring the accumulation of radiolabel in degradation products. A first‐order rate constant for co‐oxidation was extracted from the rate of accumulation of ¹⁴C in products, accounting for volumetric changes in the serum bottles due to sampling and subsequent changes to the distribution of TCE between the aqueous and gaseous phases. Of the groundwater samples evaluated from 19 wells at five sites, eight samples at three sites had ¹⁴C product accumulation rates that exceeded the accumulation rate in filter‐sterilized groundwater controls. First‐order rate constants ranged from 2.65 to 0.0066 year^?1, which is equivalent to half‐lives of 0.26 to 105 years. Groundwater samples from a few of the wells in which co‐oxidation occurred had volatile organic contaminants in addition to TCE; their presence may have induced the oxygenase enzymes that are needed for TCE co‐oxidation. ¹⁴CO₂ represented ~37% to 97% of the ¹⁴C products that accumulated; the balance of the products was soluble and non‐volatile.     

Hydrological heterogeneity of an alpine stream–lake network in Switzerland

Water source and lake landscape position can strongly influence the physico‐chemical characteristics of flowing waters over space and time. We examined the physico‐chemical heterogeneity in surface waters of an alpine stream‐lake network (>2600 m a.s.l.) in Switzerland. The catchment comprises two basins interspersed with 26 cirque lakes. The larger lakes in each basin are interconnected by streams that converge in a lowermost lake with an outlet stream. The north basin is primarily fed by precipitation and groundwater, whereas the south basin is fed mostly by glacial melt from rock glaciers. Surface flow of the entire channel network contracted by ～60% in early autumn, when snowmelt runoff ceased and cold temperatures reduced glacial outputs, particularly in the south basin. Average water temperatures were ～4 °C cooler in the south basin, and temperatures increased by about 4–6 °C along the longitudinal gradient within each basin. Although overall water conductivity was low (<27 µS cm^?1) because of bedrock geology (ortho‐gneiss), the south basin had two times higher conductivity values than the north basin. Phosphate‐phosphorus levels were below analytical detection limits, but particulate phosphorus was about four times higher in the north basin (seasonal average: 9 µg l^?1) than in the south basin (seasonal average: 2 µg l^?1). Dissolved nitrogen constituents were around two times higher in the south basin than in the north basin, with highest values averaging > 300 µg l^?1 (nitrite + nitrate‐nitrogen), whereas particulate nitrogen was approximately nine times greater in the north basin (seasonal average: 97 µg l^?1) than in the south basin (seasonal average: 12 µg l^?1). Total inorganic carbon was low (usually <0·8 mg l^?1), silica was sufficient for algal growth, and particulate organic carbon was 4·5 times higher in the north basin (average: 0·9 mg l^?1) than in the south basin (average: 0·2 mg l^?1). North‐basin streams showed strong seasonality in turbidity, particulate‐nitrogen and ‐phosphorus, and particulate organic carbon, whereas strong seasonality in south‐basin streams was observed in conductivity and dissolved nitrogen. Lake position influenced the seasonal dynamics in stream temperatures and nutrients, particularly in the groundwater/precipitation‐fed north‐basin network. Copyright © 2007 John Wiley & Sons, Ltd.     

Geochemical and isotopic evidence of a groundwater source in the Corral Canyon meadow complex,central Nevada,USA

Major inorganic ions and stable carbon and oxygen isotopes in stream water, groundwater, groundwater seeps and springs were measured in the Corral Canyon meadow complex and watershed in the Toquima Mountains of central Nevada, USA. The purpose of the study was to determine whether stream water or groundwater was the source of water that supports vegetation in the meadow complex. Water samples from the watershed and meadow complex were mixed cation–HCO₃ type. Stream water sampled at different locations in the meadow complex showed variations in temperature, pH and specific conductance. The cation–anion proportions for stream water were similar to groundwater, groundwater seeps and runoff from the meadow complex. Stable oxygen isotope ratios for stream water (?17·1 to ?17·6‰ versus VSMOW) and groundwater and groundwater seeps in the meadow site (?17·0 to ?17·7‰ versus VSMOW) were similar, and consistent with a local meteoric origin. Dissolved inorganic carbon (DIC) and the δ ¹³C_DIC for stream water (?12·1 to ?15·0‰ versus VPDB) were different from that of groundwater from the meadow complex (?15·3 to ?19·9‰ versus VPDB), suggesting different carbon evolution pathways. However, a simple model based on cation–δ ¹³C_DIC suggests that stream water was being recharged by shallow groundwater, groundwater seeps and runoff from the meadow complex. This leads to the conclusion that the source of water that supports vegetation in the meadow complex was primarily groundwater. The results of this study suggest that multiple chemical and stable carbon isotope tracers are useful in determining the source of water that supports vegetation in meadow complexes in small alpine watersheds. Copyright © 2004 John Wiley & Sons, Ltd.     

Hydro‐climatic variability and trends in Washington State for the last 50 years

Historical records of monthly streamflow and precipitation coupled with mean, minimum, and maximum air temperatures for Washington State were used to study the variation and the trend characteristics that occurred over the last 50 years (1952–2002). Results indicate that the 1967 statewide water resource assessment needs to be updated because all of the stations used in that study exhibited a decreasing trend in annual streamflow ranging from ?0·9% to ?49·3%, with an arithmetic mean of ?11·7% and a median value of ?9·8%. Furthermore, a slightly decreasing trend in annual streamflow, although not statistically significant, was detected. The decreasing streamflow magnitude was about ?1·178 mm year^?2, or 4·88 m³ s^?1 year^?1, which caused a decrease in annual streamflow in the state of about 58·9 mm, or 244 m³ s^?1. This magnitude was about 9·6% of the average annual streamflow for the entire state from 1952 to 2002. Contrastingly, the overall annual precipitation in the entire state increased 1·375 mm year^?2. Overall the annual means of daily mean, maximum, and minimum temperature increased by 0·122, 0·048, and 0·185 °C/10 years, respectively, during the study period. Thus the corresponding annual means of daily mean, maximum, and minimum temperatures increased by 0·61, 0·24, and 0·93 °C, respectively. All of these trends and magnitudes were found to vary considerably from station to station and month to month. The possible reasons resulting in these detected trends include, but are not limited to, human activities, climate variability and changes, and land use and land cover changes. Copyright © 2009 John Wiley & Sons, Ltd.     

The application of electrical conductivity as a tracer for hydrograph separation in urban catchments

Two‐component hydrograph separation was performed on 19 low‐to‐moderate intensity rainfall events in a 4·1‐km² urban watershed to infer the relative and absolute contribution of surface runoff (e.g. new water) to stormflow generation between 2001 and 2003. The electrical conductivity (EC) of water was used as a continuous and inexpensive tracer, with order of magnitude differences in precipitation (12–46 µS/cm) and pre‐event streamwater EC values (520–1297 µS/cm). While new water accounted for most of the increased discharge during storms (61–117%), the contribution of new water to total discharge during events was typically lower (18–78%) and negatively correlated with antecedent stream discharge (r² = 0·55, p < 0·01). The amount of new water was positively correlated with total rainfall (r² = 0·77), but hydrograph separation results suggest that less than half (9–46%) of the total rainfall on impervious surfaces is rapidly routed to the stream channel as new water. Comparison of hydrograph separation results using non‐conservative tracers (EC and Si) and a conservative isotopic tracer (δD) for two events showed similar results and highlighted the potential application of EC as an inexpensive, high frequency tracer for hydrograph separation studies in urban catchments. The use of a simple tracer‐based approach may help hydrologists and watershed managers to better understand impervious surface runoff, stormflow generation and non‐point‐source pollutant loading to urban streams. Copyright © 2007 John Wiley & Sons, Ltd.     

Seasonal controls on DOC dynamics in nested upland catchments in NE Scotland

Spatial and temporal variability of hydrological responses affecting surface water dissolved organic carbon (DOC) concentrations are important for determining upscaling patterns of DOC export within larger catchments. Annual and intra‐annual variations in DOC concentrations and fluxes were assessed over 2 years at 12 sites (3·40–1837 km²) within the River Dee basin in NE Scotland. Mean annual DOC fluxes, primarily correlated with catchment soil coverage, ranged from 3·41 to 9·48 g m^?2 yr^?1. Periods of seasonal (summer–autumn and winter–spring) DOC concentrations (production) were delineated and related to discharge. Although antecedent temperature mainly determined the timing of switchover between periods of high DOC in the summer‐autumn and low DOC in winter‐spring, inter‐annual variability of export within the same season was largely dependent on its associated water flux. DOC fluxes ranged from 1·39 to 4·80 g m^?2 season^?1 during summer–autumn and 1·43 to 4·15 g m^?2 season^?1 in winter–spring.Relationships between DOC areal fluxes and catchment scale indicated that mainstem fluxes reflect the averaging of highly heterogeneous inputs from contrasting headwater catchments, leading to convergent DOC fluxes at catchment sizes of ca 100 km². However, during summer–autumn periods, in contrast to winter–spring, longitudinal mainstem DOC fluxes continue to decrease, most likely because of increasing biological processes. This highlights the importance of considering seasonal as well as annual changes in DOC fluxes with catchment scale. This study increases our understanding of the temporal variability of DOC upscaling patterns reflecting cumulative changes across different catchment scales and aids modelling of carbon budgets at different stages of riverine systems. Copyright © 2010 John Wiley & Sons, Ltd.     

The electrical conductivity of eclogite in Tibet and its geophysical implications

The electrical conductivity of Tibetan eclogite was investigated at pressures of 1.5–3.5 GPa and temperatures of 500–803 K using impedance spectroscopy within a frequency range of 10-1–106 Hz. The electrical conductivity of eclogite increases with increasing temperature(which can be approximated by the Arrhenius equation), and is weakly affected by pressure. At each tested pressure, the electrical conductivity is weakly temperature dependent below ~650 K and more strongly temperature dependent above ~650 K. The calculated activation energies and volumes are 44±1 kJ/mol and-0.6±0.1 cm3/mol for low temperatures and 97±3 kJ/mol and-1.2±0.2 cm3/mol for high temperatures, respectively. When applied to the depth range of 45–100 km in Tibet, the laboratory data give conductivities on the order of 10-1.5–10-4.5 S/m, within the range of geophysical conductivity profiles.     

Comparison of AnnAGNPS and SWAT model simulation results in USDA‐CEAP agricultural watersheds in south‐central Kansas

This study was conducted under the USDA‐Conservation Effects Assessment Project (CEAP) in the Cheney Lake watershed in south‐central Kansas. The Cheney Lake watershed has been identified as ‘impaired waters’ under Section 303(d) of the Federal Clean Water Act for sediments and total phosphorus. The USDA‐CEAP seeks to quantify environmental benefits of conservation programmes on water quality by monitoring and modelling. Two of the most widely used USDA watershed‐scale models are Annualized AGricultural Non‐Point Source (AnnAGNPS) and Soil and Water Assessment Tool (SWAT). The objectives of this study were to compare hydrology, sediment, and total phosphorus simulation results from AnnAGNPS and SWAT in separate calibration and validation watersheds. Models were calibrated in Red Rock Creek watershed and validated in Goose Creek watershed, both sub‐watersheds of the Cheney Lake watershed. Forty‐five months (January 1997 to September 2000) of monthly measured flow and water quality data were used to evaluate the two models. Both models generally provided from fair to very good correlation and model efficiency for simulating surface runoff and sediment yield during calibration and validation (correlation coefficient; R², from 0·50 to 0·89, Nash Sutcliffe efficiency index, E, from 0·47 to 0·73, root mean square error, RMSE, from 0·25 to 0·45 m³ s^?1 for flow, from 158 to 312 Mg for sediment yield). Total phosphorus predictions from calibration and validation of SWAT indicated good correlation and model efficiency (R² from 0·60 to 0·70, E from 0·63 to 0·68) while total phosphorus predictions from validation of AnnAGNPS were from unsatisfactory to very good (R² from 0·60 to 0·77, E from ? 2·38 to 0·32). The root mean square error–observations standard deviation ratio (RSR) was estimated as excellent (from 0·08 to 0·25) for the all model simulated parameters during the calibration and validation study. The percentage bias (PBIAS) of the model simulated parameters varied from unsatisfactory to excellent (from 128 to 3). This study determined SWAT to be the most appropriate model for this watershed based on calibration and validation results. Copyright © 2008 John Wiley & Sons, Ltd.     

A Preliminary Study of Chromophoric Dissolved Organic Matter (CDOM) in Lake Taihu,a Shallow Subtropical Lake in China

The optical properties and spatial distribution of chromophoric dissolved organic matter (CDOM) in Meiliang Bay of Lake Taihu were evaluated and compared to the results in literature. Concentrations of dissolved organic carbon (DOC) ranged from 8.75 to 20.19 mg L^?1 with an average of (13.10 ± 3.51) mg L^?1. CDOM absorption coefficients a(λ) at 280 nm, 355 nm, and 440 nm were in the range 11.28...33.46 m^?1 (average (20.95 ± 5.52) m^?1), 2.42...7.90 m^?1 (average (4.92 ± 1.29) m^?1), and 0.65...2.44 m^?1 (average (1.46 ± 0.44) m^?1), respectively. In general, CDOM absorption coefficient and DOC concentration were found to decrease away from the river inflow to Meiliang Bay towards the lake center. The values of the DOC‐specific absorption coefficients a*(λ), given as absorption coefficient related to mass concentration of organic carbon (C) ranged from 0.28 to 0.47 L mg^?1 m^?1 at 355 nm. The determination coefficients between CDOM absorption and DOC concentration decreased with the increase of wavelength from 280 to 550 nm. The linear regression relationship between CDOM absorption at 280 nm and DOC concentration was following: a(280 nm) = 1.507 L mg^?1 m^?1 · DOC + 1.215 m^?1. The spectral slope S values were dependent on the wavelength range used in the regression. The estimated S values decreased with increasing wavelength range used. A significant negative linear relationship was found between CDOM absorption coefficients, DOC‐specific absorption coefficients and estimated S values especially in longer wavelength range. The linear regression relationship between DOC‐specific absorption coefficients at 440 nm and estimated S values during the wavelength range from 280 to 500 nm was following: a*(440 nm) = (–0.021 μm · S + 0.424) L mg^?1 m^?1.