Sorption of imidazolium-based ionic liquids to aquatic sediments

Ionic liquids (ILs) have received much attention as "green" alternatives to traditional solvents because they do not evaporate, eliminating concerns over fugitive emissions. However, if ionic liquids are used in industrial applications, they may enter aquatic systems via effluent, and their fate and transport may be influenced by sorption to sediments. In this study, we conducted batch mixing experiments with four alkylmethylimidizolium-based ILs and four types of aquatic sediments to asses the capacity for natural aquatic sediments to remove these chemicals from the water column. The concentration isotherms were non linear with point estimates of the distribution coefficient (K(d)) decreasing with increasing concentration. Apparent distribution coefficients ranged from 7.9 to 95.7l kg(-1) at an initial concentration of 0.5mM and were positively related to sediment organic matter (SOM) content. These K(d) values indicate that the ILs did not sorb strongly to the tested sediments. Increased alkyl chain length did not lead to increased sorption suggesting that hydrophobic interactions were not the most important sorption mechanism. We conclude that aquatic sediments have a limited capacity to sorb alkylmethylimidazolium ILs and that the transport of these contaminants in aquatic systems will not be strongly attenuated by sediments.     

Are rivers just big streams? A pulse method to quantify nitrogen demand in a large river

Given recent focus on large rivers as conduits for excess nutrients to coastal zones, their role in processing and retaining nutrients has been overlooked and understudied. Empirical measurements of nutrient uptake in large rivers are lacking, despite a substantial body of knowledge on nutrient transport and removal in smaller streams. Researchers interested in nutrient transport by rivers (discharge >10000 L/s) are left to extrapolate riverine nutrient demand using a modeling framework or a mass balance approach. To begin to fill this knowledge gap, we present data using a pulse method to measure inorganic nitrogen. (N) transport and removal in the Upper Snake River, Wyoming, USA (seventh order, discharge 12000 L/s). We found that the Upper Snake had surprisingly high biotic demand relative to smaller streams in the same river network for both ammonium (NH4+) and nitrate (NO3-). Placed in the context of a meta-analysis of previously published nutrient uptake studies, these data suggest that large rivers may have similar biotic demand for N as smaller tributaries. We also found that demand for different forms of inorganic N (NH4+ vs. NO3-) scaled differently with stream size. Data from rivers like the Upper Snake and larger are essential for effective water quality management at the scale of river networks. Empirical measurements of solute dynamics in large rivers are needed to understand the role of whole river networks (as opposed to stream reaches) in patterns of nutrient export at regional and continental scales.     

Denitrification and the nitrogen budget of a reservoir in an agricultural landscape.

Denitrification is an important process in aquatic sediments, but its role has not been assessed in the N mass balance of upper-Midwestern (USA) reservoirs that receive large agricultural riverine N inputs. We used a 4400-ha reservoir to determine the role of denitrification in the N mass balance and effectiveness in reducing downstream transport of NO(3-)N. Sediment denitrification was (1) measured monthly (March 2002-March 2003) at eight sites in the Lake Shelbyville reservoir in central Illinois using the acetylene inhibition, chloramphenicol technique, (2) scaled to the overall reservoir and compared to N not accounted for in a mass balance, and (3) estimated indirectly using long-term (1981-2003) mass balances of N in the reservoir. Denitrification rates in the reservoir were high during spring and early summer of 2002, when maximum NO(3-)N concentrations were measured (10-14 mg NO(3-)N/L). We estimated that denitrification for the year was between 2580 and 5150 Mg N. Missing N from the mass balance was 3004 Mg N, suggesting that sediment denitrification was the sink. Areal rates of sediment denitrification in the reservoir ranged from 62 to 225 g N x m(-2) x yr(-1), with rates a function of both denitrification intensity (microg N x g dry mass x h(-1)) and the overall mass of sediment present. From 1981 to 2003 the average NO(3-)N inlet flux was 8900 Mg N/yr. About 58% of the total NO(3-)N input was removed, and annual NO(3-)N removed as a percentage of inputs was significantly related to reservoir retention time (average = 0.36 yr for the 23 years, range = 0.21-0.84 yr). By scaling denitrification in Lake Shelbyville to other reservoirs in Illinois, we estimated a sink of 48900 Mg N/yr. When combined with estimated in-stream denitrification, 60900 Mg N/yr was estimated to be removed by sediment denitrification. This reduces riverine export from Illinois to the Gulf of Mexico, where the flux during the 1990s was about 244000 Mg N/yr, and illustrates the importance of reservoir denitrification as an N sink in Midwestern agricultural landscapes.     

Floodplain restoration enhances denitrification and reach-scale nitrogen removal in an agricultural stream

Streams of the agricultural Midwest, USA, export large quantities of nitrogen, which impairs downstream water quality, most notably in the Gulf of Mexico. The two-stage ditch is a novel restoration practice, in which floodplains are constructed alongside channelized ditches. During high flows, water flows across the floodplains, increasing benthic surface area and stream water residence time, as well as the potential for nitrogen removal via denitrification. To determine two-stage ditch nitrogen removal efficacy, we measured denitrification rates in the channel and on the floodplains of a two-stage ditch in north-central Indiana for one year before and two years after restoration. We found that instream rates were similar before and after the restoration, and they were influenced by surface water NO3- concentration and sediment organic matter content. Denitrification rates were lower on the constructed floodplains and were predicted by soil exchangeable NO3- concentration. Using storm flow simulations, we found that two-stage ditch restoration contributed significantly to NO3- removal during storm events, but because of the high NO3- loads at our study site, < 10% of the NO3- load was removed under all storm flow scenarios. The highest percentage of NO3- removal occurred at the lowest loads; therefore, the two-stage ditch's effectiveness at reducing downstream N loading will be maximized when the practice is coupled with efforts to reduce N inputs from adjacent fields.     

Implementing Innovative Drainage Management Practices in the Mississippi River Basin to Enhance Nutrient Reductions

In the Mississippi River Basin (MRB), practices that enhance drainage (e.g., channelization, tile drainage) are necessary management tools in order to maintain optimal agricultural production in modern farming systems. However, these practices facilitate, and may speed the delivery of excess nutrients and sediments to downstream water bodies via agricultural streams and ditches. These nonpoint sources contribute to elevated nutrient loading in the Gulf of Mexico, which has been linked to widespread hypoxia and associated ecological and economic problems. Research suggests agricultural drainage ditches are important links between farm fields and downstream ecosystems, and application of new management practices may play an important role in the mitigation of water quality impairments from agricultural watersheds. In this article, we describe how researchers and producers in the MRB are implementing and validating novel best management practices (BMPs) that if used in tandem could provide producers with continued cropping success combined with improved environmental protection. We discuss three BMPs — low‐grade weirs, slotted inlet pipes, and the two‐stage ditch. While these new BMPs have improved the quality of water leaving agricultural landscapes, they have been validated solely in isolation, at opposite ends of the MRB. These BMPs have similar function and would greatly benefit from stacked incorporation across the MRB to the benefit of the basin as a whole.     

Two‐Stage Ditch Floodplains Enhance N‐Removal Capacity and Reduce Turbidity and Dissolved P in Agricultural Streams

Two‐stage ditches represent an emerging management strategy in artificially drained agricultural landscapes that mimics natural floodplains and has the potential to improve water quality. We assessed the potential for the two‐stage ditch to reduce sediment and nutrient export by measuring water column turbidity, nitrate (NO₃^?), ammonium (NH₄⁺), and soluble reactive phosphorus (SRP) concentrations, and denitrification rates. During 2009‐2010, we compared reaches with two‐stage floodplains to upstream reaches with conventional trapezoid design in six agricultural streams. At base flow, these short two‐stage reaches (<600 m) reduced SRP concentrations by 3‐53%, but did not significantly reduce NO₃^? concentrations due to very high NO₃^? loads. The two‐stage also decreased turbidity by 15‐82%, suggesting reduced suspended sediment export during floodplain inundation. Reach‐scale N‐removal increased 3‐24 fold during inundation due to increased bioreactive surface area with high floodplain denitrification rates. Inundation frequency varied with bench height, with lower benches being flooded more frequently, resulting in higher annual N‐removal. We also found both soil organic matter and denitrification rates were higher on older floodplains. Finally, influence of the two‐stage varied among streams and years due to variation in stream discharge, nutrient loads, and denitrification rates, which should be considered during implementation to optimize potential water quality benefits.     

A hydrochemical elucidation of the groundwater composition under domestic and irrigated land in Jaipur City

The study area Jaipur, the capital of Rajasthan, is one of the famous metropolises in India. In order to know the suitability of groundwater for domestic and irrigation purposes in Jaipur City, groundwater samples were composed of 15 stations during post-monsoon time of the year 2007–2008 (Nov 2007 to Feb 2008) and were analyzed for physicochemical characters. The physicochemical parameters of groundwater participate a significant role in classifying and assessing water quality. A preliminary characterization, carried out using the piper diagram, shows the different hydrochemistry of the sampled groundwater. This diagram shows that most of the groundwater samples fall in the field of calcium-magnesium-chloride-sulfate type (such water has permanent hardness) of water. Data are plotted on the US Salinity Laboratory diagram, which illustrates that most of the groundwater samples fall in the field of C2S1 and C3S1, which can be used for irrigation on almost all type of soil with little danger of exchangeable sodium. Based on the analytical results, chemical indices like %Na, SAR, and RSC were calculated which show that most of the samples are good for irrigation.     

Timber harvest transforms ecological roles of salmon in southeast Alaska rain forest streams

Although species commonly modify habitats and thereby influence ecosystem structure and function, the factors governing the ecological importance of these modifications are not well understood. Pacific salmon have repeatedly been shown to positively influence the abundance of benthic biota by annually transferring large quantities of nutrients from marine systems to the nutrient-poor freshwaters in which they spawn. Conversely, other studies have demonstrated that salmon can negatively influence the abundance of freshwater biota, an effect attributed to bioturbation during upstream migration and nest construction. The factors determining which of these contrasting ecological effects predominates are unknown, including how human activities, such as land use, influence ecological responses to salmon. We sampled a key basal food resource, sediment biofilm, in seven southeast Alaskan streams impacted to varying degrees by timber harvest. Biofilm abundance (measured as chlorophyll a and ash-free dry mass) was positively related to timber-harvest intensity prior to salmon arrival. However, during the salmon run, an inverse relationship emerged of more abundant biofilm in less-harvested watersheds. Among-stream variability in biofilm response to salmon was largely explained by sediment particle size, which was larger in less-harvested watersheds. Collectively, these results suggest that, by altering stream sediment size, timber harvest transformed the dominant effect of salmon from nutrient enrichment to physical disturbance, thus modifying nutrient linkages between marine and freshwater ecosystems.     

Transport and fate of nitrate in headwater agricultural streams in Illinois

Nitrogen inputs to the Gulf of Mexico have increased during recent decades and agricultural regions in the upper Midwest, such as those in Illinois, are a major source of N to the Mississippi River. How strongly denitrification affects the transport of nitrate (NO(3)-N) in Illinois streams has not been directly assessed. We used the nutrient spiraling model to assess the role of in-stream denitrification in affecting the concentration and downstream transport of NO(3)-N in five headwater streams in agricultural areas of east-central Illinois. Denitrification in stream sediments was measured approximately monthly from April 2001 through January 2002. Denitrification rates tended to be high (up to 15 mg N m(-2) h(-1)), but the concentration of NO(3)-N in the streams was also high (>7 mg N L(-1)). Uptake velocities for NO(3)-N (uptake rate/concentration) were lower than reported for undisturbed streams, indicating that denitrification was not an efficient N sink relative to the concentration of NO(3)-N in the water column. Denitrification uptake lengths (the average distance NO(3)-N travels before being denitrified) were long and indicated that denitrification in the streambed did not affect the transport of NO(3)-N. Loss rates for NO(3)-N in the streams were <5% d(-1) except during periods of low discharge and low NO(3)-N concentration, which occurred only in late summer and early autumn. Annually, most NO(3)-N in these headwater sites appeared to be exported to downstream water bodies rather than denitrified, suggesting previous estimates of N losses through in-stream denitrification may have been overestimated.     

The Influence of Two‐Stage Ditches with Constructed Floodplains on Water Column Nutrients and Sediments in Agricultural Streams

The two‐stage ditch is a novel management practice originally implemented to increase bank stability through floodplain restoration in channelized agricultural streams. To determine the effects of two‐stage construction on sediment and nutrient loads, we monitored turbidity, and also measured total suspended solids (TSS), dissolved inorganic nitrogen (N) species, and phosphorus (P) after two‐stage ditch construction in reference and manipulated reaches of four streams. Turbidity decreased during floodplain inundation at all sites, but TSS and P, soluble reactive phosphorus (SRP) and total phosphorus (TP) decreased only in the two‐stage ditches with longer duration of inundation. Both TSS and TP were positively correlated within individual streams, but neither were correlated with turbidity. Phosphorus was elevated in the stream to which manure was applied adjacent to the two‐stage reach, but not the reference reach, suggesting that landscape nutrient management plans could restrict nutrient transport to the stream, ultimately determining the efficacy of instream management practices. In addition, ammonium and nitrate decreased in two‐stage reaches with lower initial N concentrations. Overall, results suggest that turbidity, TSS, and TP were reduced during floodplain inundation, but the two‐stage alone may not be effective for managing high inorganic N loads.