Daily variability of river concentrations and fluxes: indicators based on the segmentation of the rating curve

The variability of water chemistry on a daily scale is rarely addressed due to the lack of records. Appropriate tools, such as typologies and dimensionless indicators, which permit comparisons between stations and between river materials, are missing. Such tools are developed here for daily concentrations (C), specific fluxes or yields (Y) and specific river flow (q). The data set includes 128 long‐term daily records, for suspended particulate matter (SPM), total dissolved solids (TDS), dissolved and total nutrients, totalling 1236 years of records. These 86 river basins (10³–10⁶ km²) cover a wide range of environmental conditions in semi‐arid and temperate regions. The segmentation—truncation of C–q rating curves into two parts at median flows (q₅₀) generates two exponents (b_50inf and b_50sup) that are different for 66% of the analysed rating curves. After segmentation, the analysis of records results in the definition of nine major C–q types combining concentrating, diluting or stable patterns, showing inflexions, chevron and U shapes. SPM and TDS are preferentially distributed among a few types, while dissolved and total nutrients are more widely distributed. Four dimensionless indicators of daily variability combine median (C₅₀, Y₅₀), extreme (C₉₉, Y₉₉) and flow‐weighted (C*, Y*) concentrations and yields (e.g. C₉₉/C₅₀, Y*/Y₅₀). They vary over two to four orders of magnitude in the analysed records, discriminating stations and river material. A second set of four indicators of relative variability [e.g. (Y*/Y₅₀)/(q*/q₅₀)], takes into account the daily flow variability, as expressed by q*/q₅₀ and q₉₉/q₅₀, which also vary over multiple orders of magnitude. The truncated exponent b_50sup is used to describe fluxes at higher flows accounting for 75% (TDS) to 97% (SPM) of interannual fluxes. It ranges from ? 0·61 to + 1·86 in the database. It can be regarded as the key amplificator (positive b_50sup) or reductor (negative b_50sup) of concentrations or yields variability. C₅₀, Y₅₀, b_50sup can also be estimated in discrete surveys, which provides a new perspective for quantifying and mapping water quality variability at daily scale. Copyright © 2011 John Wiley & Sons, Ltd.     

Adjoint method for the optimum planning of industrial pollutant sources

The deterioration of air quality is threatening the life and health of people. Scientists in China and other countries have done a great deal of research work on the details of air pollution and the methods of preven-tion and control during the past decades. Up to now, most of the achievements are concentrated on the techniques of controlling pollutant sources and the programs of reduction, which focus on the improve-ment of air quality and the restoration of environment. The techniques of con…     

Pathlines of pollutant migration in groundwater of the Visakhapatnam urban area,India

The groundwater regime in the north‐western part of the Visakhapatnam urban area was polluted as early as 1981 by discharge of untreated industrial effluent from a Hindustan Polymers Limited (HPL) plant. A total dissolved solids (TDS) concentration of surficial effluent up to 6500 mg/l and of groundwater in the range 3000–4200 mg/l has been reported in the environs of the HPL plant during May 1992. Groundwater occurs under water table conditions. The groundwater flow model was simulated as a single layer aquifer, using MODFLOW and FLOWPATH computer models. Aquifer parameters were estimated and the value of effective porosity assumed. The water table configuration was mapped in May 1981 using 33 observation wells. The calibrated hydraulic head distribution was used to compute the velocity field using the effective porosity values. The flow paths of groundwater migration from the source locations up to 2002 AD were predicted. Pathlines of particles in the groundwater indicated a predominant north‐east and south‐west migration of groundwater pollution in the area. Copyright © 1999 John Wiley & Sons, Ltd.     

内蒙古达里诺尔湖流域地表水和地下水环境同位素特征及补给关系

为了探明达里诺尔湖流域地表水与地下水的氢(H)、氧(O)同位素的变化特征及相互补给关系,于2013年对达里诺尔湖及其周围的河水、井水、泉水中H、O同位素进行了取样分析,并结合总溶解性固体悬浮物(TDS)和区域水文地质对达里诺尔湖流域的补给关系进行讨论分析.结果表明:1)河水、泉水、井水中H、O同位素的值基本落在全球雨水线上,湖水H、O同位素落在全球雨水线的右下方,说明河水、井水、泉水没有发生蒸发分馏,而湖水则发生较大程度的蒸发分馏;对达里诺尔湖流域地表水与地下水的H、O同位素进行回归模拟,得出该区域的蒸发趋势线方程:δD=4.8753δ18O-20.139(n=32,R2=0.9968).蒸发线表明,这些水样具有相同水源的特征.2)从实地考察发现,泉水补给河水,泉水和河水补给湖水,同时井水、泉水和河水有相似的δD、δ18O和TDS值,且不随季节变化而变化,推断达里诺尔湖附近地下水补给湖水;区域水文地质条件亦证明达里诺尔湖周边地下水补给湖水.     

Hydrochemical behaviour of dissolved nitrogen and carbon in a headwater stream of the Canadian Shield: relevance of antecedent soil moisture conditions

This paper examines the impact of contrasting antecedent soil moisture conditions on the hydrochemical response, here the changes in dissolved nitrogen (NO₃^?, NH₄⁺ and dissolved organic nitrogen (DON)) and dissolved organic carbon (DOC) concentrations, of a first‐order stream during hydrological events. The study was performed in the Hermine, a 5 ha forested watershed of the Canadian Shield. It focused on a series of eight precipitation events (spring, summer and fall) sampled every 2 or 3 h and showing contrasted antecedent moisture conditions. The partition of the eight events between two groups (dry or wet) of antecedent moisture conditions was conducted using a principal component analysis (PCA). The partition was controlled (first axis explained 86% of the variability) by the antecedent streamflow, the streamflow to precipitation ratio Q/P and by the antecedent groundwater depth. The mean H⁺, NO₃^?, NH₄⁺, total dissolved nitrogen and DOC concentrations and electrical conductivity values in the stream were significantly higher following dry antecedent conditions than after wetter conditions had prevailed in the Hermine, although the temporal variability was high (17 to 138%). At the event scale, a significantly higher proportion of the changes in DON, NO₃^?, and DOC concentrations in the stream was explained by temporal variations in discharge compared with the seasonal and annual scales. Two of the key hydrochemical features of the dry events were the synchronous changes in DOC and flow and the frequent negative relationships between discharge and NO₃^?. The DON concentrations were much less responsive than DOC to changes in discharge, whereas NH was not in phase with streamflow. During wet events, the synchronicity between streamflow and DON or NO₃^? was higher than during dry events and discharge and NO₃^? were generally positively linked. Based on these observations, the hydrological behaviour of the Hermine is conceptually compatible with a two‐component model of shallow (DON and DOC rich; variable NO₃^?) and deep (DON and DOC poor; variable NO₃^?) subsurface flow. The high NO₃^? and DOC levels measured at the early stages of dry events reflected the contribution from NO₃^?‐rich groundwaters. The contribution of rapid surface flow on water‐repellent soil materials located close to the stream channel is hypothesized to explain the DOC levels. An understanding of the complex interactions between antecedent soil moisture conditions, the presence of soil nutrients available for leaching and the dynamics of soil water flow paths during storms is essential to explain the fluxes of dissolved nitrogen and carbon in streams of forested watersheds. Copyright © 2007 John Wiley & Sons, Ltd.     

Temporal and spatial variations in the discharge and dissolved organic carbon of drip waters in Beijing Shihua Cave,China

To detect the causal relationship between cave drip waters and stalagmite laminae, which have been used as a climate change proxy, three drip sites in Beijing Shihua Cave were monitored for discharge and dissolved organic carbon (DOC). Drip discharges and DOC were determined at 0 to 14‐day intervals over the period 2004–2006. Drip discharges show two types of response to surface precipitation variations: (1) a rapid response; and (2) a time‐lagged response. Intra‐annual variability in drip discharge is significantly higher than inter‐annual variability. The content of DOC in all drip waters varies inter‐ and intra‐annually and has good correlation with drip water discharge at the rapid response sites. High DOC was observed in July and August in the three years observed. The flushing of soil organic matter is dependent upon the intensity of rain events. The DOC content of drip water increases sharply above a threshold rainfall intensity (>50 mm d^?1) and shows several pulses corresponding with intense rain events (>25 mm d^?1). The DOC content was lower and less variable during the dry period than during the rainy period. The shape of DOC peak also varies from year to year as it is influenced by the intensity and frequency of rainfall. The different drip sites show marked differences in DOC response, which are dominated by hydrological behaviour linked to the recharge of the soil and karst micro‐fissure/porosity network. The results explain why not all stalagmite laminae are consistent with climate changes and suggest that the structure of the rainy season events could be preserved in speleothems. Copyright © 2008 John Wiley & Sons, Ltd.     

太湖梅梁湾藻华暴发-消退周期表层水体溶解性有机质分子特征

人类活动引起的富营养化对太湖的碳循环模式可能产生严重影响,精细描述太湖藻华暴发-消退周期的溶解性有机质分子是了解太湖碳库动态变化的关键.本研究利用傅立叶变换离子回旋共振质谱技术,以太湖北部梅梁湾2017年5月至2018年5月的表层水体为研究对象,解析藻华暴发-消退周期溶解性有机质的来源和分子组成特征,进而理解浮游藻类异常增殖对水体溶解性有机质的影响及其在区域碳循环中的角色.研究结果表明,藻华暴发期浮游藻类生产力显著增加,使得表层水体的溶解性有机质从含量到分子组成均发生剧烈改变.含量上表现为溶解性有机碳浓度升高,分子组成上表现为CHO类化合物和以脂肪族类化合物为代表的活性组分占比增加,特征化合物以相对高饱和度和高含氧的小质量数分子为主.而在藻华消退期,随着藻类有机质贡献的减少和有机质降解过程的持续进行,含量上表现为溶解性有机碳浓度下降,分子组成上表现为CHOS、CHONS类化合物和富羧酸脂环类化合物等惰性分子占比增加,特征化合物以大质量数分子和相对低饱和度和低含氧的小质量数分子为主.研究结果表明,太湖水体的溶解性有机质分子组成在藻华暴发期受藻类有机质输入控制,在消退期受藻类有机质降解的影...     

Dissolved organic matter in surface runoff in the Loess Plateau of China: The role of rainfall events and land-use

Exploring the chemical characterization of dissolved organic matter (DOM) is important for understanding the fate of laterally transported organic matter in watersheds. We hypothesized that differences in water-extractable organic matter (WEOM) in soils of varying land uses and rainfall events may significantly affect the quality and the quantity of stream DOM. To test our hypotheses, characteristics of rainfall-runoff DOM and WEOM of source materials (topsoil from different land uses and gullies, as well as typical vegetation) were investigated at two adjacent catchments in the Loess Plateau of China, using ultraviolet–visible absorbance and excitation emission matrix fluorescence with parallel factor analysis (PARAFAC). Results indicated that land-use types may significantly affect the chemical composition of soil WEOM, including its aromaticity, molecular weight, and degree of humification. The PARAFAC analysis demonstrated that the soils and stream water were dominated by terrestrial/allochthonous humic-like substances and microbial transformable humic-like fluorophores. Shifts in the fluorescence properties of stream DOM suggested a pronounced change in the relative proportion of allochthonous versus autochthonous material under different rainfall patterns and land uses. For example, high proportions of forestland could provide more allochthonous DOM input. This study highlights the relevance of soils and hydrological dynamics on the composition and fluxes of DOM issuing from watersheds. The composition of DOM in soils was influenced by land-use type. Precipitation patterns influenced the proportion of terrestrial versus microbial origins of DOM in surface runoff. Contributions of allochthonous, terrestrially derived DOM inputs were highest from forested landscapes.     

Multivariate adaptive regression splines for estimating riverine constituent concentrations

Regression-based methods are commonly used for riverine constituent concentration/flux estimation, which is essential for guiding water quality protection practices and environmental decision making. This paper developed a multivariate adaptive regression splines model for estimating riverine constituent concentrations (MARS-EC). The process, interpretability and flexibility of the MARS-EC modelling approach, was demonstrated for total nitrogen in the Patuxent River, a major river input to Chesapeake Bay. Model accuracy and uncertainty of the MARS-EC approach was further analysed using nitrate plus nitrite datasets from eight tributary rivers to Chesapeake Bay. Results showed that the MARS-EC approach integrated the advantages of both parametric and nonparametric regression methods, and model accuracy was demonstrated to be superior to the traditionally used ESTIMATOR model. MARS-EC is flexible and allows consideration of auxiliary variables; the variables and interactions can be selected automatically. MARS-EC does not constrain concentration-predictor curves to be constant but rather is able to identify shifts in these curves from mathematical expressions and visual graphics. The MARS-EC approach provides an effective and complementary tool along with existing approaches for estimating riverine constituent concentrations.     

Modelling spatial variations in dissolved oxygen in fine‐grained streams under uncertainty

This paper presents a novel triple‐layer model, called VART DO‐3L, for simulation of spatial variations in dissolved oxygen (DO) in fine‐grained streams, characterized by a fluid mud (fluff or flocculent) layer (an advection‐dominated storage zone) as the interface between overlying stream water and relatively consolidated streambed sediment (a diffusion‐dominated storage zone). A global sensitivity analysis is conducted to investigate the sensitivity of VART DO‐3L model input parameters. Results of the sensitivity analysis indicate that the most sensitive parameter is the relative size of the advection‐dominated storage zones (A_s/A), followed by a lumped reaction term (R) for the flocculent layer, biological reaction rate (μ_o) in diffusive layer and biochemical oxygen demand concentration (L) in water column. In order to address uncertainty in model input parameters, Monte Carlo simulations are performed to sample parameter values and to produce various parameter combinations or cases. The VART DO‐3L model is applied to the Lower Amite River in Louisiana, USA, to simulate vertical and longitudinal variations in DO under the cases. In terms of longitudinal variation, the DO level decreases from 7.9 mg l at the Denham Springs station to about 2.89 mg l^?1 at the Port Vincent station. In terms of vertical variation, the DO level drops rapidly from the overlying water column to the advection‐dominated storage zone and further to the diffusive layer. The DO level (C_F) in the advective layer (flocculent layer) can reach as high as 40% of DO concentration (C) in the water column. The VART DO‐3L model may be applied to similar rivers for simulation of spatial variations in DO level. Copyright © 2014 John Wiley & Sons, Ltd.