Performance of the National Water Model in Iowa Using Independent Observations

This paper explores the performance of the analysis‐and‐assimilation configuration of the National Water Model (NWM) v1.0 in Iowa. The NWM assimilates streamflow observations from the United States Geological Survey (USGS), which increases the performance but also limits the available data for model evaluation. In this study, Iowa Flood Center Bridge Sensors (IFCBS) data provided an independent nonassimilated dataset for evaluation analyses. The authors compared NWM outputs for the period between May 2016 and April 2017, with two datasets: USGS streamflow and velocity observations; Stage and streamflow data from IFCBS. The distribution of Spearman rank correlation (r_s), Nash–Sutcliffe efficiency (E), and Kling–Gupta efficiency (KGE) provided quantification of model performance. We found the performance was linked with the spatial scale of the basins. Analysis at USGS gauges showed the strongest performance in large (>10,000 km²) basins (r_s = 0.9, E = 0.9, KGE = 0.8), with some decrease at small (<1,000 km²) basins (r_s = 0.6, E = ?0.25, KGE = ?0.2). Analysis with independent IFCBS observations was used to report performance at large basins (r_s = 0.6, KGE = 0.1) and small basins (r_s = 0.2, KGE = ?0.4). Data assimilation improves simulations at downstream basins. We found differences in the characterization of the model and observed data flow velocity distributions. The authors recommend checking the connection of USGS gauges and NHDPlus reaches for selected locations where performance is weak.     

Storage of CO2 in saline aquifers: Effects of gravity, viscous, and capillary forces on amount and timing of trapping

CO₂ can be effectively immobilized during CO₂ injection into saline aquifers by residual trapping – also known as capillary trapping – a process resulting from capillary snap-off of isolated CO₂ bubbles. Simulations of CO₂ injection were performed to investigate the interplay of viscous and gravity forces and capillary trapping of CO₂. Results of those simulations show that gas injection processes in which gravitational forces are weak compared to viscous forces (low gravity number N_gv) trap significantly more CO₂ than do flows with strong gravitational forces relative to the viscous forces (high N_gv). The results also indicate that over a wide range of gravity numbers (N_gv), significant fractions of the trapping of CO₂ can occur relatively quickly. The amount of CO₂ that is trapped after injection ceases is demonstrated to correlate with N_gv. For some simulated displacements, effects of capillary pressure and aquifer dip angle on the amount and the rate of trapping are reported. Trapping increases when effects of capillary pressure and aquifer inclination are included in the model. Finally we show that injection schemes such as alternating injection of brine and CO₂ or brine injection after CO₂ injection can also enhance the trapping behavior.     

Comparison of biosorbents with inorganic sorbents for removing copper(II) from aqueous solutions

In comparison with several other reported inorganic sorbents, Camellia tree leaf and primary sludge obtained from a settling tank as a pretreatment to the activated sludge system in a Hong Kong sewage treatment plant were evaluated for removing Cu(II) from aqueous solutions. Experimental data were modeled by the Langmuir isotherm equation to estimate the maximum sorption capacity (q_max). Results show that, at pH 5.6, biosorbents, Camellia tree leaf and primary sludge in particular, exert higher sorption capacities (q_max > 40 mg g⁻¹) than inorganic sorbents, Na-montmorillonite (q_max = 33.3 mg g⁻¹), fly ash (q_max = 18.8 mg g⁻¹), and goethite powder (10.3 mg g⁻¹). Furthermore, a pseudo second-order kinetic model was found to properly describe the experimental data for both bio- and inorganic sorbents. Sorption of Cu(II) on the Camellia tree leaf and primary sludge were much faster than that on the inorganic sorbents. In addition, desorption tests revealed that the desorption capacities of the two biomaterials are higher than the other selected materials; and much more Cu(II) can be retrieved from the Cu(II)-loaded biosorbents. Finally, increasing solution pH was found to greatly increase q_max and accelerate sorption processes.     

Effects of Land Use and Climate Change on Stream Temperature II: Threshold Exceedance Duration Projections for Freshwater Mussels

We developed a stochastic hourly stream temperature model (SHSTM) to estimate probability of exceeding given threshold temperature (T) for specified durations (24 and 96 h) to assess potential impacts on freshwater mussels in the upper Tar River, North Carolina. Simulated daily mean stream T from climate change (CC) and land‐use (LU) change simulations for 2021‐2030 and 2051‐2060 were used as input to the SHSTM. Stream T observations in 2010 revealed only two sites with T above 30°C for >24 h and Ts were never >31°C for more than 24 h at any site. The SHSTM suggests that the probability, P, that T will exceed 32°C for at least 96 h in a given year increased from P = 0, in the 20th Century, to P = 0.05 in 2021‐2030 and to P = 0.14 in 2051‐2060. The SHSTM indicated that CC had greater effects on P for 24 and 96 h durations than LU change. Increased P occurred primarily in higher order stream segments in the downstream reaches of the basin. The SHSTM indicated that hourly stream T responded to LU change on the daily scale and did not affect stream T for durations >24 h. The SHSTM indicated that known thermal thresholds for freshwater mussels could be exceeded within the next 50 years in many parts of the upper Tar River basin in North Carolina, which could have negative consequences on the recruitment of freshwater mussels.     

Plant and Soil Responses to High and Low Diversity Grassland Restoration Practices

The USDA’s Conservation Reserve Program (CRP) has predominantly used only a few species of dominant prairie grasses (CP2 practice) to reduce soil erosion, but recently has offered a higher diversity planting practice (CP25) to increase grassland habitat quality. We quantified plant community composition in CP25 and CP2 plantings restored for 4 or 8 years and compared belowground properties and processes among restorations and continuously cultivated soils in southeastern Nebraska, USA. Relative to cultivated soils, restoration increased soil microbial biomass (P = 0.033), specifically fungi (P < 0.001), and restored soils exhibited higher rates of carbon (C) mineralization (P = 0.010). High and low diversity plantings had equally diverse plant communities; however, CP25 plantings had greater frequency of cool-season (C₃) grasses (P = 0.007). Older (8 year) high diversity restorations contained lower microbial biomass (P = 0.026), arbuscular mycorrhizal fungi (AMF) biomass (P = 0.003), and C mineralization rates (P = 0.028) relative to 8 year low diversity restorations; older plantings had greater root biomass than 4 year plantings in all restorations (P = 0.001). Low diversity 8 year plantings contained wider root C:N ratios, and higher soil microbial biomass, microbial community richness, AMF biomass, and C mineralization rate relative to 4 year restorations (P < 0.050). Net N mineralization and nitrification rates were lower in 8 year than 4 year high diversity plantings (P = 0.005). We attributed changes in soil C and N pools and fluxes to increased AMF associated with C₄ grasses in low diversity plantings. Thus, reduced recovery of AMF in high diversity plantings restricted restoration of belowground microbial diversity and microbially-mediated soil processes over time.     

Mineralization of integrated gasification combined-cycle power-station wastewater effluent by a photo-fenton process

The aim of this work was to study the mineralization of wastewater effluent from an integrated-gasification combined-cycle (IGCC) power station sited in Spain to meet the requirements of future environmental legislation. This study was done in a pilot plant using a homogeneous photo-Fenton oxidation process with continuous addition of H₂O₂ and air to the system.The mineralization process was found to follow pseudo-first-order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The NNs model reproduced the experimental data to within a 90% confidence level and allowed the simulation of the process for any values of the parameters within the experimental range studied. At the optimum conditions (H₂O₂ flow rate = 120 mL/h, [Fe(II)] = 7.6 mg/L, pH = 3.75 and air flow rate = 1 m³/h), a 90% mineralization was achieved in 150 min.Determination of the hydrogen peroxide consumed and remaining in the water revealed that 1.2 mol of H₂O₂ was consumed per each mol of total organic carbon removed from solution. This result confirmed that an excess of dissolved H₂O₂ was needed to achieve high mineralization rates, so continuous addition of peroxide is recommended for industrial application of this process.Air flow slightly improved the mineralization rate due to the formation of peroxo-organic radicals which enhanced the oxidation process.     

Estimation of “environmentally sensitive” dispersal ratios for chemical dispersants used in crude oil spill control

The toxicities of two dispersants (Biosolve and OSD 9460), Forcados light crude oil and their mixtures based on ratios 6:1, 9:1, and 12:1 (v/v) were evaluated against the juvenile stage of African catfish, Clarias gariepinus, in laboratory bioassays. On the basis of the derived toxicity indices, Biosolve (96-h LC₅₀ = 0.211 μl/l) was found to be about 27,284 times more toxic than crude oil (96-h LC₅₀ = 5.757 ml/l) and 6,450 times more toxic than OSD 9460 (96-h LC₅₀ = 1.361 ml/l). OSD 9460 was also found to be four times more toxic than crude oil when acting alone against C. gariepinus. Toxicity evaluations of the mixtures of crude oil/dispersants mixtures varied, depending largely upon the proportion of addition of the mixture components. The interactions between mixture of crude oil and Biosolve at the test ratios of 6:1, 9:1, and 12:1 were found to conform with the model of synergism (SR = 7,655, 14,876, and 8,792, respectively), and the mixtures were therefore more toxic than the crude oil acting singly. Similarly, the interactions between mixture of crude oil and OSD 9460 at the test ratios of 6:1 and 9:1 also conformed to the model of synergism (SR = 2.2 and 1.84, respectively). Interactions between the dispersant OSD 9460 and the crude oil at test ratio 12:1, however, conformed to the model of antagonism (SR = 0.84), indicating that the mixture was less toxic than crude oil acting alone. The results of the emulsification potential of OSD 9460 and Biosolve [measured in terms of optical transmittance (%)] prepared at the dispersal ratios 6:1, 9:1, and 12:1 revealed that the dispersal ratio of 6:1 achieved the highest emulsification of the crude oil with optical transmittance value of 4% and 6%, respectively. Estimation of an “environmentally sensitive” dispersal ratio for OSD 9460 and Biosolve revealed the optimum dispersal ratio for OSD 9460 range between ratios 7.5:1 and 9:1, while for Biosolve such an optimum dispersal ratio was indeterminate within the range of test dispersal ratios. The implications of these results in setting manufacturer’s and regulatory dispersal ratios for chemical dispersants used for oil spill control were discussed.     

Water/acid gas interfacial tensions and their impact on acid gas geological storage

Acid gas geological disposal is a promising process to reduce CO₂ atmospheric emissions and an environment-friendly and economic alternative to the transformation of H₂S into sulphur by the Claus process. Acid gas confinement in geological formations is to a large extent controlled by the capillary properties of the water/acid–gas/caprock system, because a significant fraction of the injected gas rises buoyantly and accumulates beneath the caprock. These properties include the water/acid gas interfacial tension (IFT), to which the so-called capillary entry pressure of the gas in the water-saturated caprock is proportional. In this paper we present the first ever systematic water/acid gas IFT measurements carried out by the pendant drop technique under geological storage conditions. We performed IFT measurements for water/H₂S systems over a large range of pressure (up to P = 15 MPa) and temperature (up to T = 120 °C). Water/H₂S IFT decreases with increasing P and levels off at around 9–10 mN/m at high T (≥70 °C) and P (>12 MPa). The latter values are around 30–40% of water/CO₂ IFTs, and around 20% of water/CH₄ IFTs at similar T and P conditions. The IFT between water and a CO₂ + H₂S mixture at T = 77 °C and P > 7.5 MPa is observed to be approximately equal to the molar average IFT of the water/CO₂ and water/H₂S binary mixtures. Thus, when the H₂S content in the stored acid gas increases the capillary entry pressure decreases, together with the maximum height of acid gas column and potential storage capacity of a given geological formation. Hence, considerable attention should be exercised when refilling with a H₂S-rich acid gas a depleted gas reservoir, or a depleted oil reservoir with a gas cap: in the case of hydrocarbon reservoirs that were initially (i.e., at the time of their discovery) close to capillary leakage, acid gas leakage through the caprock will inevitably occur if the refilling pressure approaches the initial reservoir pressure.     

Effects of Land Use and Sample Location on Nitrate‐Stream Flow Hysteresis Descriptors during Storm Events

The U.S. Geological Survey's New Jersey and Iowa Water Science Centers deployed ultraviolet‐visible spectrophotometric sensors at water‐quality monitoring sites on the Passaic and Pompton Rivers at Two Bridges, New Jersey, on Toms River at Toms River, New Jersey, and on the North Raccoon River near Jefferson, Iowa to continuously measure in‐stream nitrate plus nitrite as nitrogen (NO₃ + NO₂) concentrations in conjunction with continuous stream flow measurements. Statistical analysis of NO₃ + NO₂ vs. stream discharge during storm events found statistically significant links between land use types and sampling site with the normalized area and rotational direction of NO₃ + NO₂‐stream discharge (N‐Q) hysteresis patterns. Statistically significant relations were also found between the normalized area of a hysteresis pattern and several flow parameters as well as the normalized area adjusted for rotational direction and minimum NO₃ + NO₂ concentrations. The mean normalized hysteresis area for forested land use was smaller than that of urban and agricultural land uses. The hysteresis rotational direction of the agricultural land use was opposite of that of the urban and undeveloped land uses. An r² of 0.81 for the relation between the minimum normalized NO₃ + NO₂ concentration during a storm vs. the normalized NO₃ + NO₂ concentration at peak flow suggested that dilution was the dominant process controlling NO₃ + NO₂ concentrations over the course of most storm events.     

Biohythane production from pineapple peel using Methanosarcina mazei enhanced with palm oil mill effluent (POME) sludge in single-stage anaerobic digestion

Biohythane production via single-stage anaerobic digestion (AD) is an effective way for sustainable energy recovery from lignocellulosic biomass. In this paper, biohythane was produced through the AD process from pineapple peel waste substrate using purely cultured Methanosarcina mazei with the enhancement of palm oil mill effluent (POME) sludge as the inoculum. This study focuses on the effects of the lignocellulosic pre-treatment method, the addition of POME sludge into M. mazei culture medium as inoculum, and various operational conditions (food to microorganisms (F/M) ratios, temperature, pH) on gas production performances. The experimental results indicate that these parameters influenced the efficiency of biohythane production by producing the peak maximum biohythane production rate values (HPR_max) and (MPR_max), H₂:CH₄ = 1.93:0.67 L/L-d, and biohythane yield (HY) and (MY), H₂:CH₄ = 1.18:0.55 mL/L-substrate. This study demonstrates that biohythane gas (H₂ + CH₄ + CO₂) production from pineapple waste can be accelerated by M. mazei only with the enhancement of POME sludge through single-stage AD system under mesophilic batch process conditions.     

STABLE HYDROGEN AND OXYGEN ISOTOPE COMPOSITION OF PRECIPITATION IN NORTHEASTERN COLORADO1

ABSTRACT: Where data are available, hydrologic studies may use precipitation's stable oxygen and hydrogen isotope composition to investigate streamflow, ground water/surface water interaction, and ground water recharge. Paleoclimate studies utilize the δ¹⁸O_{precipitation}‐T_air relationship, in conjunction with lake sediments, fossils, or old ground waters, for example, to estimate pale‐otemperatures. Ecological studies utilize precipitation and soil water isotope composition to track moisture uptake in plants, and to trace species migration patterns. Such studies require that the isotopic composition of precipitation be known. Oxygen‐18 (δ¹⁸O) and deuterium (δ²H) data for precipitation are lacking in the semi‐arid portion of the north‐central U.S. Great Plains, and thus there is a need to establish additional meteoric water lines as isotope input functions across the region, as well as to develop better understanding of the isotopic climate linkages that control oxygen and hydrogen isotope ratios in precipitation. This study determined the δ¹⁸O and δ²H composition of precipitation in the Pawnee Grasslands of northeastern Colorado from 1994 through 1998 using archived National Atmospheric Deposition Program samples. The resulting local water line follows the relationship δ²H = 7.86 δ¹⁸O‐7.66, and the data show a δ¹⁸O_weekly ‐ T_weekly relationship of δ¹⁸O = 0.560‐T (°C)‐18.8.     

Arsenic uptake and phytotoxicity of T-aman rice (<Emphasis Type="Italic">Oryza sativa</Emphasis> L.) grown in the As-amended soil of Bangladesh

A pot-culture experiment was conducted in open-field conditions with highly cultivated locally transplanted (T) aman rice (Oryza sativa L.) named BR-22 in arsenic (As)-amended soil (0, 1.0, 5.0, 10.0, 20.0, 30.0, 40.0 and 50.0 mg kg⁻¹ As) of Bangladesh to see the effect of As on the growth, yield and metal uptake of rice. Arsenic was applied to soil in the form of sodium arsenate (Na₂HAsO₄). Arsenic affected the plant height, tiller and panicle numbers, grain and straw yield of T-aman rice significantly (P ≤ 0.05). The grain As uptake of T-aman rice was found to increase with increase of As in soil and a high grain As uptake was observed in the treatments of 30–50 mg kg⁻¹ As-containing soil. These levels exceed the food hygiene concentration limit of 1.0 mg kg⁻¹ As. However, the straw As uptake varied significantly (P ≤ 0.05) from a low concentration of As in soil (5 mg kg⁻¹) and the highest uptake was noticed in 20 mg kg⁻¹ As treatment.     

PRISM vs. CFSR Precipitation Data Effects on Calibration and Validation of SWAT Models

Precipitation is one of the most important drivers in watershed models. Our objective was to compare two sources of interpolated precipitation data in terms of their effect on calibration and validation of two Soil and Water Assessment Tool (SWAT) models. One model was a suburban watershed in metropolitan Atlanta, Georgia. The precipitation sources were Parameter‐elevation Relationships on Independent Slopes Model (PRISM) data on a 4‐km grid and climate forecast system reanalysis (CFSR) data on a 38‐km grid. The PRISM data resulted in a better fit to the calibration data (Nash Sutcliffe efficiency [NSE] = 0.64, Kling‐Gupta efficiency [KGE] = 0.74, p‐factor = 0.84, and r‐factor = 0.43) than the CFSR data (NSE = 0.47, KGE = 0.53, p‐factor = 0.67, and r‐factor = 0.39). Validation results were similar. Sensitive parameters were similar in both the PRISM and CFSR models, but fitted values indicated more rapid groundwater flow to the streams with the PRISM data. The same comparison was made in the Big Creek watershed located approximately 1,000 km away, in central Louisiana. Results were similar with a more responsive groundwater system indicating PRISM data may produce better predictions of streamflow because of a more accurate estimate of rainfall within a watershed or because of a denser grid. Our study implies PRISM is providing a better estimate than CFSR of precipitation within a watershed when rain gauge data are not available, resulting in more accurate simulations of streamflows at the watershed outlet. Editor's note: This paper is part of the featured series on SWAT Applications for Emerging Hydrologic and Water Quality Challenges. See the February 2017 issue for the introduction and background to the series.     

Response of Soil Inorganic Nitrogen to Land Use and Topographic Position in the Cofre de Perote Volcano (Mexico)

This study addressed the effects of land use and slope position on soil inorganic nitrogen and was conducted in small watersheds. The study covered three land use types: tropical cloud forest, grassland, and coffee crop. To conduct this research, typical slope small watersheds were chosen in each land use type. Slopes were divided into three positions: shoulder, backslope, and footslope. At the center of each slope position, soil sampling was carried out. Soil inorganic nitrogen was measured monthly during a period of 14 months (July 2005–August 2006) with 11 observations. Significant differences in soil NH₄ ⁺–N and NO₃ ⁻–N content were detected for both land use and sampling date effects, as well as for interactions. A significant slope position-by-sampling date interaction was found only in coffee crop for NO₃ ⁻–N content. In tropical cloud forest and grassland, high soil NH₄ ⁺–N and low NO₃ ⁻–N content were recorded, while soil NO₃ ⁻–N content was high in coffee crop. Low NO₃ ⁻–N contents could mean a substantial microbial assimilation of NO₃ ⁻–N, constituting an important mechanism for nitrogen retention. Across the entire land use set, the relationship between soil temperature and soil inorganic N concentration was described by an exponential decay function (N = 33 + 2459exp^−0.23T, R ² = 0.44, P < 0.0001). This study also showed that together, soil temperature and gravimetric soil water content explained more variation in soil inorganic N concentration than gravimetric soil water content alone.     

Modeling Discharge Rates Using a Coupled Modeled Approach for the Merced River in Yosemite National Park

This study describes the application of the NASA version of the Carnegie‐Ames‐Stanford Approach (CASA) ecosystem model coupled with a surface hydrologic routing scheme previously called the Hydrological Routing Algorithm (HYDRA) to model monthly discharge rates from 2000 to 2007 on the Merced River drainage in Yosemite National Park, California. To assess CASA‐HYDRA's capability to estimate actual water flows in extreme precipitation years, the focus of this study is the 2007 water year, which was very dry, and the 2005 water year, which was a moderately wet year in the historical record. Prior to comparisons to gauge records, CASA‐HYDRA snowmelt algorithms were modified with equations from the U.S. Department of Agriculture Snowmelt‐Runoff Model (SRM), which has been designed to predict daily streamflow in mountain basins where snowmelt is a major runoff factor. Results show that model predictions closely matched monthly flow rates at the Pohono Bridge gauge station (USGS#11266500), with R² = 0.67 and Nash‐Sutcliffe (E) = 0.65. By subdividing the upper Merced River basin into subbasins with high spatial resolution in the gridded modeling approach, we were able to determine which biophysical characteristics in the Sierra differed to the largest degree in extreme low‐flow and high‐flow years. Average elevation and snowpack accumulation were found to be the most important explanatory variables to understand subbasin contributions to monthly discharge rates.     

Nutrients and suspended solids in dry weather and storm flows from a tropical catchment with various proportions of rural and urban land use

The results of an investigation characterizing the nutrients and suspended solids contained in stormwater from Kranji Catchment in Singapore are reported in this paper. Stormwater samples were collected from 4 locations and analyzed for the following eleven analytes: TOC, DOC, TN, TDN, NH₄⁺, NO₂⁻ + NO₃⁻ (NO_x), TP, TDP, OP, SiO₂ and TSS. Stormwater was sampled from catchments with various proportions of rural and urban land use, including forested areas, grassed areas, agricultural and residential and commercial areas. The event mean concentrations (EMCs) of nutrients and TSS from sampling stations which have agricultural land use activities upstream were found to be higher. Comparison of site EMCs (SMCs) with published data showed that the SMCs of the nutrients and TSS are generally higher than SMCs reported for forested areas but lower than published SMCs for urban areas. Positive correlations (p < 5%) were found between loading and peak flow at locations most impacted by ubanisation or agricultural activities. Correlation between loading and rainfall variables was less distinct. EMC was found to correlate less with rainfall and flow variables compared to pollutant loading. Unlike loading, no consistent pattern exists linking EMC to any particular storm or flow variable in any of the catchments. Lastly, positive correlations were obtained between the particulate forms of nitrogen and phosphorus and TSS.     

Empirical Estimation of Stream Discharge Using Channel Geometry in Low‐Gradient,Sand‐Bed Streams of the Southeastern Plains

Manning's equation is used widely to predict stream discharge (Q) from hydraulic variables when logistics constrain empirical measurements of in‐bank flow events. Uncertainty in Manning's roughness (n_M) is the major source of error in natural channels, and sand‐bed streams pose difficulties because flow resistance is affected by flow‐dependent bed configuration. Our study was designed to develop and validate models for estimating Q from channel geometry easily derived from cross‐sectional surveys and available GIS data. A database was compiled consisting of 484 Q measurements from 75 sand‐bed streams in Alabama, Georgia, South Carolina, North Carolina (Southeastern Plains), and Florida (Southern Coastal Plain), with six New Zealand streams included to develop statistical models to predict Q from hydraulic variables. Model error characteristics were estimated with leave‐one‐site‐out jackknifing. Independent data of 317 Q measurements from 55 Southeastern Plains streams indicated the model (Q = A_cR_H^0.6906S^0.1216; where A_c is the channel area, R_H is the hydraulic radius, and S is the bed slope) best predicted Q, based on Akaike's information criterion and root mean square error. Models also were developed from smaller Q range subsets to explore if subsets increased predictive ability, but error fit statistics suggested that these were not reasonable alternatives to the above equation. Thus, we recommend the above equation for predicting in‐bank Q of unbraided, sandy streams of the Southeastern Plains.     

The Use of Carbon and Nitrogen Isotopes to Study Watershed Erosion Processes1

Abstract:  Tracer studies are needed to better understand watershed soil erosion and calibrate watershed erosion models. For the first time, stable nitrogen and carbon isotopes (δ¹⁵N and δ¹³C) and the carbon to nitrogen atomic ratio (C/N) natural tracers are used to investigate temporal and spatial variability of erosion processes within a sub‐watershed. Temporal variability was assessed by comparing δ¹⁵N, δ¹³C, and C/N of eroded‐soils from a non‐equilibrium erosion event immediately following freezing and thawing of surface soils with two erosion events characterized by equilibrium conditions with erosion downcutting. Spatial variability was assessed for the equilibrium events by using the δ¹⁵N and δ¹³C signatures of eroded‐soils to measure the fraction of eroded‐soil derived from rill/interrill erosion on upland hillslopes as compared to headcut erosion on floodplains. In order to perform this study, a number of tasks were carried out including: (1) sampling source‐soils from upland hillslopes and floodplains, (2) sampling eroded‐soils with an in situ trap in the stream of the sub‐watershed, (3) isotopic and elemental analysis of the samples using isotope ratio mass spectrometry, (4) fractioning eroded‐soil to its upland rill/interrill and floodplain headcut end‐members using an unmixing model within a Bayesian Markov Chain Monte Carlo framework, and (5) evaluating tracer unmixing model results by comparison with process‐based erosion prediction models for rill/interrill and headcut erosion processes. Results showed that finer soil particles eroded during the non‐equilibrium event were enriched in δ¹⁵N and δ¹³C tracers and depleted in C/N tracer relative to coarser soil particles eroded during the equilibrium events. Correlation of tracer signature with soil particle size was explainable based on known biogeochemical processes. δ¹⁵N and δ¹³C were also able to distinguish between upland rill/interrill erosion and floodplain headcut erosion, which was due to different plant cover at the erosion sources. Results from the tracer unmixing model highlighted future needs for coupling rill/interrill and headcut erosion prediction models.     

Equilibrium studies of copper ion adsorption onto palm kernel fibre

The equilibrium sorption of copper ions from aqueous solution using a new adsorbent, palm kernel fibre, has been studied. Palm kernel fibre is obtained in large amounts as a waste product of palm oil production. Batch equilibrium studies were carried out and system variables such as solution pH, sorbent dose, and sorption temperature were varied. The equilibrium sorption data was then analyzed using the Langmuir, Freundlich, Dubinin–Radushkevich (D–R) and Temkin isotherms. The fit of these isotherm models to the equilibrium sorption data was determined, using the linear coefficient of determination, r², and the non-linear Chi-square, χ² error analysis.The results revealed that sorption was pH dependent and increased with increasing solution pH above the pH_PZC of the palm kernel fibre with an optimum dose of 10 g/dm³. The equilibrium data were found to fit the Langmuir isotherm model best, with a monolayer capacity of 3.17 × 10^?4 mol/g at 339 K. The sorption equilibrium constant, K_a, increased with increasing temperature, indicating that bond strength between sorbate and sorbent increased with temperature and sorption was endothermic. This was confirmed by the increase in the values of the Temkin isotherm constant, B₁, with increasing temperature. The Dubinin–Radushkevich (D–R) isotherm parameter, free energy, E, was in the range of 15.7–16.7 kJ/mol suggesting that the sorption mechanism was ion exchange. Desorption studies showed that a high percentage of the copper was desorbed from the adsorbent using acid solutions (HCl, HNO₃ and CH₃COOH) and the desorption percentage increased with acid concentration. The thermodynamics of the copper ions/palm kernel fibre system indicate that the process is spontaneous and endothermic.     

Factors affecting nitrate distribution in shallow groundwater under a beef farm in South Eastern Ireland

Groundwater contamination was characterised using a methodology which combines shallow groundwater geochemistry data from 17 piezometers over a 2 yr period in a statistical framework and hydrogeological techniques. Nitrate–N (NO₃-N) contaminant mass flux was calculated across three control planes (rows of piezometers) in six isolated plots. Results showed natural attenuation occurs on site although the method does not directly differentiate between dilution and denitrification. It was further investigated whether NO₃-N concentration in shallow groundwater (<5 m below ground level) generated from an agricultural point source on a 4.2 ha site on a beef farm in SE Ireland could be predicted from saturated hydraulic conductivity (K_sat) measurements, ground elevation (m Above Ordnance Datum), elevation of groundwater sampling (screen opening interval) (m AOD) and distance from a dirty water point pollution source. Tobit regression, using a background concentration threshold of 2.6 mg NO₃-N L⁻¹ showed, when assessed individually in a step wise procedure, K_sat was significantly related to groundwater NO₃-N concentration. Distance of the point dirty water pollution source becomes significant when included with K_sat in the model. The model relationships show areas with higher K_sat values have less time for denitrification to occur, whereas lower K_sat values allow denitrification to occur. Areas with higher permeability transport greater NO₃-N fluxes to ground and surface waters. When the distribution of Cl⁻ was examined by the model, K_sat and ground elevation had the most explanatory power but K_sat was not significant pointing to dilution having an effect. Areas with low NO₃ concentration and unaffected Cl⁻ concentration points to denitrification, low NO₃ concentration and low Cl⁻ chloride concentration points to dilution and combining these findings allows areas of denitrification and dilution to be inferred. The effect of denitrification is further supported as mean groundwater NO₃-N was significantly (P < 0.05) related to groundwater N₂/Ar ratio, redox potential (Eh), dissolved O₂ and N₂ and was close to being significant with N₂O (P = 0.08). Calculating contaminant mass flux across more than one control plane is a useful tool to monitor natural attenuation. This tool allows the identification of hot spot areas where intervention other than natural attenuation may be needed to protect receptors.