WATERSHED FUNCTIONS1

ABSTRACT: Watershed functions that dominate the hydrologic environment are identified and discussed. Hydrological and ecological functions are considered in relation to the storm and annual hydrographs, and to water quality. Two integrative watershed responses to these functions are also articulated. Since most of the Earth's water is in storage, consideration of the hydrologic cycle as movement between water storage sites enhances this functional and response characterization of the watershed which, in turn, suggests guidance and direction for the restoration of watershed functions.     

Development of Layered Sediment Structure and its Effects on Pore Water Transport and Hyporheic Exchange

Hyporheic exchange is known to provide an important control on nutrient and contaminant fluxes across the stream-subsurface interface. Similar processes also mediate interfacial transport in other permeable sediments. Recent research has focused on understanding the mechanics of these exchange processes and improving estimation of exchange rates in natural systems. While the structure of sediment beds obviously influences pore water flow rates and patterns, little is known about the interplay of typical sedimentary structures, hyporheic exchange, and other transport processes in fluvial/alluvial sediments. Here we discuss several processes that contribute to local-scale sediment heterogeneity and present results that illustrate the interaction of overlying flow conditions, the development of sediment structure, pore water transport, and stream-subsurface exchange. Layered structures are shown to develop at several scales within sediment beds. Surface sampling is used to analyze the development of an armor layer in a sand-and-gravel bed, while innovative synchrotron-based X-ray microtomography is used to observe patterns of grain sorting within sand bedforms. We show that layered bed structures involving coarsening of the bed surface increase interfacial solute flux but produce an effective anisotropy that favors horizontal pore water transport while limiting vertical penetration.     

Improving the Urban Stream Restoration Effort: Identifying Critical Form and Processes Relationships

Stream restoration projects are often based on morphological form or stream type and, as a result, there needs to be a clear tie established between form and function of the stream. An examination of the literature identifies numerous relationships in naturally forming streams that link morphologic form and stream processes. Urban stream restoration designs often work around infrastructure and incorporate bank stabilization and grade control structures. Because of these imposed constraints and highly altered hydrologic and sediment discharge regimens, the design of urban channel projects is rather unclear. In this paper, we examine the state of the art in relationships between form and processes, the strengths and weaknesses of these existing relationships, and the current lack of understanding in applying these relationships in the urban environment. In particular, we identify relationships that are critical to urban stream restoration projects and provide recommendations for future research into how this information can be used to improve urban stream restoration design. It is also suggested that improving the success of urban restoration projects requires further investigation into incorporating process-based methodologies, which can potentially reduce ambiguity in the design and the necessity of using an abundant amount of in-stream structures.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Elimination of diclofenac from water using irradiation technology

The effluents of wastewater treatment plants, usually directly emitted to the environment, often contain the anti-inflammatory drug diclofenac (DCF). The paper investigates DCF elimination using irradiation technology. Hydroxyl radical and hydrated electron reactive intermediates resulting from water radiolysis effectively degrade DCF and strongly reduce the toxicity of the solutions. OH attaches to one of the rings of DCF, and hydroxylated molecules, 2,6-dichloroaniline and quinoid type compounds are the products. Hydrated electron adds to the chlorine atom containing ring, in the reaction quinoid type compounds and 4-chloroacridine form. At a 0.1 mM DCF concentration, a ∼1 kGy absorbed dose is needed for the degradation of DCF molecules, but for mineralization of the products (in presence of O₂) an order of magnitude higher dose is required.For irradiation of wastewater after biological treatment a ∼1 kGy dose is suggested. At this dose DCF and other drugs or metabolites present at μg L⁻¹ level are eliminated together with microorganism deactivation.     

春季生物作用对山地岩溶池水地球化学特征的影响

岩溶水文系统对外界环境变化敏感,使得岩溶区水质存在昼夜、小时甚至分钟等尺度的变化.许多地表水体都会经历p H值、溶解性气体、微量元素以及其他水化学指标的昼夜变化.重庆金佛山水房泉及受其补给的水池地处海拔2 050 m的山地岩溶区,具有温带气候特征.通过对水房泉泉水(以下简称泉水)及水池进行为期3 d的昼夜监测,以期探究春季生物作用对岩溶池水地球化学的影响.研究发现,在昼夜时间尺度上,泉水地球化学指标基本稳定,未表现出昼夜变化,池水地球化学指标化学表现出了昼夜波动,但水温、溶解氧、p H值、电导率等物理化学指标昼夜变化幅度较小.在不同的天气条件下,水温、溶解氧、Cl-等昼夜变化幅度存在差别;池水二氧化碳分压(p CO2)、Ca2+、DIC白天降低、晚上升高,方解石饱和指数(SIc)相反;这些指标的变化受控于温度、碳酸盐岩矿物的溶解与沉淀、水生植物光合作用与呼吸作用;通过亨利常数的计算,发现水温变化对p CO2变化的影响仅占0.79%~10.01%,水温、碳酸盐岩沉淀等物理因素对DIC损失量的贡献率为39%,水生植物光合作用的贡献率为61%.     

基于质谱技术的在线大气颗粒物来源与污染过程解析研究——以江苏省淮安市为例

通过大气细颗粒物实时在线源解析技术(质谱直接测量法)采集录入淮安市市区部分特征污染源排放成分谱,对淮安市大气细颗粒物进行在线源解析,获取高时间分辨的颗粒物源解析结果,分析颗粒物来源、季度变化和重污染天气的污染过程,评估形成重污染过程的污染影响因子和影响程度,为区域大气污染综合整治提供重要目标指向,同时也为淮安环境空气PM2.5重度污染实时预警与监控、大气污染源减排方案评估、污染事件监控等提供有效的在线监测技术平台.     

Transformations of particles, metal elements and natural organic matter in different water treatment processes

Characterizing natural organic matter （NOM）, particles and elements in different water treatment processes can give a useful information to optimize water treatment operations. In this article, transformations of particles, metal elements and NOM in a pilot-scale water treatment plant were investigated by laser light granularity system, particle counter, glass-fiber membrane filtration, inductively coupled plasma-optical emission spectroscopy, ultra filtration and resin absorbents fractionation. The results showed that particles, NOM and trihalomethane formation precursors were removed synergistically by sequential treatment of different processes. Preozonation markedly changed the polarity and molecular weight of NOM, and it could be conducive to the following coagulation process through destabilizing particles and colloids; mid-ozonation enhanced the subsequent granular activated carbon （GAC） filtration process by decreasing molecular weight of organic matters. Coagulation-flotation and GAC were more efficient in removing fixed suspended solids and larger particles; while sand-filtration was more efficient in removing volatile suspended solids and smaller particles. Flotation performed better than sedimentation in terms of particle and NOM removal. The type of coagulant could greatly affect the performance of coagulation-flotation. Pre-hydrolyzed composite coagulant （HPAC） was superior to FeCl3 concerning the removals of hydrophobic dissolved organic carbon and volatile suspended solids. The leakages of flocs from sand-filtration and microorganisms from GAC should be mitigated to ensure the reliability of the whole treatment system.     

Spatial and temporal variations in groundwater nitrate at an intensive dairy farm in south-east Ireland: Insights from stable isotope data

Achievement of at least “good ecological status” in all waterbodies under the EU Water Framework Directive by 2015 will in some cases be a challenge. The twin challenge is to manage expectations of policy makers for such waterbodies as to a realistic length of time required for improvement in water quality. Hence, understanding the source, transformation processes and residence time of nitrate in a hydrological system is an essential part of meeting such challenges. On a dairy farm with 24 shallow groundwater wells, the dual isotopic composition of nitrate (δ¹⁵N and δ¹⁸O) was used to clarify nitrate sources, to assess spatial and temporal variability in nitrate concentrations and to determine if and where denitrification was occurring. Vertical travel time was estimated to correlate nitrate concentrations with management practices. Organically derived nitrogen was the predominant source contributing to groundwater nitrate concentrations. Denitrification was identified as prevalent within specific regions of the study site. The distinct low temporal variability in the isotopic data suggests constancy among nitrate sources and processes over time across the study site. Vertical travel times of up to 3 years were estimated on site indicating the influence of recent management practices on nitrate concentrations. Very slow horizontal migration of groundwater (decades) indicates a legacy of older management practices. Stable isotope techniques, together with an understanding of time lag, provide an extra mechanism to test the efficacy of monitoring and mitigation programmes.