Understanding hydrochemical processes using 3D models and hydrochemical facies in Wairau Plain groundwater, Marlborough

Three dimensional models and groundwater quality are combined to better understand and conceptualise groundwater systems in complex geological settings in the Wairau Plain, Marlborough. Hydrochemical facies, which are characteristic of distinct evolutionary pathways and a common hydrologic history of groundwaters, are identified within geological formations to assess natural water-rock interactions, redox potential and human agricultural impact on groundwater quality in the Wairau Plain.

Hydrochemical processes in lowland rivers: insights from in situ, high-resolution monitoring

This paper introduces new insights into the hydrochemical functioning of lowland river systems using field-based spectrophotometric and electrode technologies. The streamwater concentrations of nitrogen species and phosphorus fractions were measured at hourly intervals on a continuous basis at two contrasting sites on tributaries of the River Thames – one draining a rural catchment, the River Enborne, and one draining a more urban system, The Cut. The measurements complement those from an existing network of multi-parameter water quality sondes maintained across the Thames catchment and weekly monitoring based on grab samples. The results of the sub-daily monitoring show that streamwater phosphorus concentrations display highly complex dynamics under storm conditions dependent on the antecedent catchment wetness, and that diurnal phosphorus and nitrogen cycles occur under low flow conditions. The diurnal patterns highlight the dominance of sewage inputs in controlling the streamwater phosphorus and nitrogen concentrations at low flows, even at a distance of 7 km from the nearest sewage treatment works in the rural River Enborne. The time of sample collection is important when judging water quality against ecological thresholds or standards. An exhaustion of the supply of phosphorus from diffuse and multiple septic tank sources during storm events was evident and load estimation was not improved by sub-daily monitoring beyond that achieved by daily sampling because of the eventual reduction in the phosphorus mass entering the stream during events. The results highlight the utility of sub-daily water quality measurements and the discussion considers the practicalities and challenges of in situ, sub-daily monitoring.

Hydrochemical evolution and groundwater flow processes in the Galilee and Eromanga basins, Great Artesian Basin, Australia: A multivariate statistical approach

The Galilee and Eromanga basins are sub-basins of the Great Artesian Basin (GAB). In this study, a multivariate statistical approach (hierarchical cluster analysis, principal component analysis and factor analysis) is carried out to identify hydrochemical patterns and assess the processes that control hydrochemical evolution within key aquifers of the GAB in these basins. The results of the hydrochemical assessment are integrated into a 3D geological model (previously developed) to support the analysis of spatial patterns of hydrochemistry, and to identify the hydrochemical and hydrological processes that control hydrochemical variability. In this area of the GAB, the hydrochemical evolution of groundwater is dominated by evapotranspiration near the recharge area resulting in a dominance of the Na–Cl water types. This is shown conceptually using two selected cross-sections which represent discrete groundwater flow paths from the recharge areas to the deeper parts of the basins. With increasing distance from the recharge area, a shift towards a dominance of carbonate (e.g. Na–HCO3 water type) has been observed. The assessment of hydrochemical changes along groundwater flow paths highlights how aquifers are separated in some areas, and how mixing between groundwater from different aquifers occurs elsewhere controlled by geological structures, including between GAB aquifers and coal bearing strata of the Galilee Basin. The results of this study suggest that distinct hydrochemical differences can be observed within the previously defined Early Cretaceous–Jurassic aquifer sequence of the GAB. A revision of the two previously recognised hydrochemical sequences is being proposed, resulting in three hydrochemical sequences based on systematic differences in hydrochemistry, salinity and dominant hydrochemical processes. The integrated approach presented in this study which combines different complementary multivariate statistical techniques with a detailed assessment of the geological framework of these sedimentary basins, can be adopted in other complex multi-aquifer systems to assess hydrochemical evolution and its geological controls.

Seasonal and spatial variations in rare earth elements to identify inter-aquifer linkages and recharge processes in an Australian catchment

With the aim of elucidating the seasonal behaviour of rare earth elements (REEs), surface and groundwaters were collected under dry and wet conditions in different hydrological units of the Teviot Brook catchment (Southeast Queensland, Australia). Sampled waters showed a large degree of variability in both REE abundance and normalised patterns. Overall REE abundance ranged over nearly three orders of magnitude, and was consistently lower in the sedimentary bedrock aquifer (18ppt<∑REE<477ppt) than in the other hydrological systems studied. Abundance was greater in springs draining rhyolitic rocks (∑REE=300 and 2054ppt) than in springs draining basalt ranges (∑REE=25 and 83ppt), yet was highly variable in the shallow alluvial groundwater (16ppt<∑REE<5294ppt) and, to a lesser extent, in streamwater (85ppt<∑REE<2198ppt). Generally, waters that interacted with different rock types had different REE patterns. In order to obtain an unbiased characterisation of REE patterns, the ratios between light and middle REEs (R(M/L)) and the ratios between middle and heavy REEs (R(H/M)) were calculated for each sample. The sedimentary bedrock aquifer waters had highly evolved patterns depleted in light REEs and enriched in middle and heavy REEs (0.17processes and inter-aquifer mixing. They also underline the importance of conducting seasonal sampling campaigns to capture possible short-term variations in REE patterns and abundance, which is essential to enable a better understanding of hydrological and hydrochemical processes in complex geological settings

Hydrochemical Atlas of the Arctic Ocean

Introduction: Chemical composition of water determines its physical properties and character of processes proceeding in it: freezing temperature, volume of evaporation, density, color, transparency, filtration capacity, etc. Presence of chemical elements in water solution confers waters special physical properties exerting significant influence on their circulation, creates necessary conditions for development and inhabitance of flora and fauna, and imparts to the ocean waters some chemical features that radically differ them from the land waters (Alekin & Liakhin, 1984). Hydrochemical information helps to determine elements of water circulation, convection depth, makes it easier to distinguish water masses and gives additional knowledge of climatic variability of ocean conditions. Hydrochemical information is a necessary part of biological research. Water chemical composition can be the governing characteristics determining possibility and limits of use of marine objects, both stationary and moving in sea water. Subject of investigation of hydrochemistry is study of dynamics of chemical composition, i.e. processes of its formation and hydrochemical conditions of water bodies (Alekin & Liakhin 1984). The hydrochemical processes in the Arctic Ocean are the least known. Some information on these processes can be obtained in odd publications. A generalizing study of hydrochemical conditions in the Arctic Ocean based on expeditions conducted in the years 1948-1975 has been carried out by Rusanov et al. (1979). The "Atlas of the World Ocean: the Arctic Ocean" contains a special section "Hydrochemistry" (Gorshkov, 1980). Typical vertical profiles, transects and maps for different depths - 0, 100, 300, 500, 1000, 2000, 3000 m are given in this section for the following parameters: dissolved oxygen, phosphate, silicate, pH and alkaline-chlorine coefficient. The maps were constructed using the data of expeditions conducted in the years 1948-1975. The illustrations reflect main features of distribution of the hydrochemical elements for multi-year period and represent a static image of hydrochemical conditions. Distribution of the hydrochemical elements on the ocean surface is given for two seasons - winter and summer, for the other depths are given mean annual fields. Aim of the present Atlas is description of hydrochemical conditions in the Arctic Ocean on the basis of a greater body of hydrochemical information for the years 1948-2000 and using the up-to-date methods of analysis and electronic forms of presentation of hydrochemical information. The most wide-spread characteristics determined in water samples were used as hydrochemical indices. They are: dissolved oxygen, phosphate, silicate, pH, total alkalinity, nitrite and nitrate. An important characteristics of water salt composition - "salinity" has been considered in the Oceanographic Atlas of the Arctic Ocean (1997, 1998). Presentation of the hydrochemical characteristics in this Hydrochemical Atlas is wider if compared with that of the former Atlas (Gorshkov, 1980). Maps of climatic distribution of the hydrochemical elements were constructed for all the standard depths, and seasonal variability of the hydrochemical parameters is given not only for the surface, but also for the underlying standard depths up to 400 m and including. Statistical characteristics of the hydrochemical elements are given for the first time. Detailed accuracy estimates of initial data and map construction are also given in the Atlas. Calculated values of mean-root deviations, maximum and minimum values of the parameters demonstrate limits of their variability for the analyzed period of observations. Therefore, not only investigations of chemical statics are summarized in the Atlas, but also some elements of chemical dynamics are demonstrated. Digital arrays of the hydrochemical elements obtained in nodes of a regular grid are the new form of characteristics presentation in the Atlas. It should be mentioned that the same grid and the same boxes were used in the Atlas, as those that had been used by creation of the US-Russian climatic Oceanographic Atlas. It allows to combine hydrochemical and oceanographic information of these Atlases. The first block of the digital arrays contains climatic characteristics calculated using direct observational data. These climatic characteristics were not calculated in the regions without observations, and the information arrays for these regions have gaps. The other block of climatic information in a gridded form was obtained with the help of objective analysis of observational data. Procedure of the objective analysis allowed us to obtain climatic estimates of the hydrochemical characteristics for the whole water area of the Arctic Ocean including the regions not covered by observations. Data of the objective analysis can be widely used, in particular, in hydrobiological investigations and in modeling of hydrochemical conditions of the Arctic Ocean. Array of initial measurements is a separate block. It includes all the available materials of hydrochemical observations in the form, as they were presented in different sources. While keeping in mind that this array contains some amount of perverted information, the authors of the Atlas assumed it necessary to store this information in its primary form. Methods of data quality control can be developed in future in the process of hydrochemical information accumulation. It can be supposed that attitude can vary in future to the data that were rejected according to the procedure accepted in the Atlas. The hydrochemical Atlas of the Arctic Ocean is the first specialized and electronic generalization of hydrochemical observations in the Arctic Ocean and finishes the program of joint efforts of Russian and US specialists in preparation of a number of atlases for the Arctic. The published Oceanographic Atlas (1997, 1998), Atlas of Arctic Meteorology and Climate (2000), Ice Atlas of the Arctic Ocean prepared for publication and Hydrochemical Atlas of the Arctic Ocean represent a united series of fundamental generalizations of empirical knowledge of Arctic Ocean nature at climatic level. The Hydrochemical Atlas of the Arctic Ocean was elaborated in the result of joint efforts of the SRC of the RF AARI and IARC. Dr. Ye. Nikiforov was scientific supervisor of the Atlas, Dr. R. Colony was manager on behalf of the USA and Dr. L. Timokhov - on behalf of Russia.

Hydrogeology and hydrochemistry of the aquifer systems of Kuttanad area, Kerala: Their role in understanding the evolution of groundwaters

This is an attempt to understand the important factors that control the occurrence, development and hydrochemical evolution of groundwater resources in sedimentary multi aquifer systems. The primary objective of this work is an integrated study of the hydrogeology and hydrochemistry with a view to elucidate the hydrochemical evolution of groundwater resources in the aquifer systems. The study is taken up in a typical coastal sedimentary aquifer system evolved under fluvio-marine environment in the coastal area of Kerala, known as the Kuttanad. The present study has been carried out to understand the aquifer systems, their inter relationships and evolution in the Kuttanad area of Kerala. The multi aquifer systems in the Kuttanad basin were formed from the sediments deposited under fluvio-marine and fluvial depositional environments and the marine transgressions and regressions in the geological past and palaeo climatic conditions influenced the hydrochemical environment in these aquifers. The evolution of groundwater and the hydrochemical processes involved in the formation of the present day water quality are elucidated from hydrochemical studies and the information derived from the aquifer geometry and hydraulic properties. Kuttanad area comprises of three types of aquifer systems namely phreatic aquifer underlain by Recent confined aquifer followed by Tertiary confined aquifers. These systems were formed by the deposition of sediments under fluvio-marine and fluvial environment. The study of the hydrochemical and hydraulic properties of the three aquifer systems proved that these three systems are separate entities. The phreatic aquifers in the area have low hydraulic gradients and high rejected recharge. The Recent confined aquifer has very poor hydraulic characteristics and recharge to this aquifer is very low. The Tertiary aquifer system is the most potential fresh water aquifer system in the area and the groundwater flow in the aquifer is converging towards the central part of the study area (Alleppey town) due to large scale pumping of water for water supply from this aquifer system. Mixing of waters and anthropogenic interferences are the dominant processes modifying the hydrochemistry in phreatic aquifers. Whereas, leaching of salts and cation exchange are the dominant processes modifying the hydrochemistry of groundwater in the confined aquifer system of Recent alluvium. Two significant chemical reactions modifying the hydrochemistry in the Recent aquifers are oxidation of iron in ferruginous clays which contributes hydrogen ions and the decomposition of organic matter in the aquifer system which consumes hydrogen ions. The hydrochemical environment is entirely different in the Tertiary aquifers as the groundwater in this aquifer system are palaeo waters evolved during various marine transgressions and regressions and these waters are being modified by processes of leaching of salts, cation exchange and chemical reactions under strong reducing environment. It is proved that the salinity observed in the groundwaters of Tertiary aquifers are not due to seawater mixing or intrusion, but due to dissolution of salts from the clay formations and ion exchange processes. Fluoride contamination in this aquifer system lacks a regional pattern and is more or less site specific in natureThe lowering of piezometric heads in the Tertiary aquifer system has developed as consequence of large scale pumping over a long period. Hence, puping from this aquifer system is to be regulated as a groundwater management strategy. Pumping from the Tertiary aquifers with high capacity pumps leads to well failures and mixing of saline water from the brackish zones. Such mixing zones are noticed from the hydrochemical studies. This is the major aquifer contamination in the Tertiary aquifer system which requires immediate attention. Usage of pumps above 10 HP capacities in wells taping Tertiary aquifers should be discouraged for sustainable development of these aquifers. The recharge areas need to be identified precisely for recharging the aquifer systems throughartificial means.

Podzolization as a deferralitization process: dynamics and chemistry of ground and surface waters in an Acrisol-Podzol sequence of the upper Amazon Basin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Vinasse application to sugar cane fields. Effect on the unsaturated zone and groundwater at Valle del Cauca (Colombia)

Extensive application of vinasse, a subproduct from sugar cane plantations for bioethanol production, is currently taking place as a source of nutrients that forms part of agricultural management in different agroclimatic regions. Liquid vinasse composition is characterised by high variability of organic compounds and major ions, acid pH (4.7), high TDS concentration (117,416–599,400 mg L− 1) and elevated EC (14,350–64,099 μS cm− 1). A large-scale sugar cane field application is taking place in Valle del Cauca (Colombia), where monitoring of soil, unsaturated zone and the aquifer underneath has been made since 2006 to evaluate possible impacts on three experimental plots. For this assessment, monitoring wells and piezometers were installed to determine groundwater flow and water samples were collected for chemical analysis. In the unsaturated zone, tensiometers were installed at different depths to determine flow patterns, while suction lysimeters were used for water sample chemical determinations. The findings show that in the sandy loam plot (Hacienda Real), the unsaturated zone is characterised by low water retention, showing a high transport capacity, while the other two plots of silty composition presented temporal saturation due to La Niña event (2010–2011). The strong La Niña effect on aquifer recharge which would dilute the infiltrated water during the monitoring period and, on the other hand dissolution of possible precipitated salts bringing them back into solution may occur. A slight increase in the concentration of major ions was observed in groundwater (~ 5% of TDS), which can be attributed to a combination of factors: vinasse dilution produced by water input and hydrochemical processes along with nutrient removal produced by sugar cane uptake. This fact may make the aquifer vulnerable to contamination.

Multivariate statistical analysis of hydrochemical data to assess alluvial aquifer–stream connectivity during drought and flood : Cressbrook Creek, southeast Queensland, Australia

A catchment-scale multivariate statistical analysis of hydrochemistry enabled assessment of interactions between alluvial groundwater and Cressbrook Creek, an intermittent drainage system in southeast Queensland, Australia. Hierarchical cluster analyses and principal component analysis were applied to time-series data to evaluate the hydrochemical evolution of groundwater during periods of extreme drought and severe flooding. A simple three-dimensional geological model was developed to conceptualise the catchment morphology and the stratigraphic framework of the alluvium. The alluvium forms a two-layer system with a basal coarse-grained layer overlain by a clay-rich low-permeability unit. In the upper and middle catchment, alluvial groundwater is chemically similar to streamwater, particularly near the creek (reflected by high HCO3/Cl and K/Na ratios and low salinities), indicating a high degree of connectivity. In the lower catchment, groundwater is more saline with lower HCO3/Cl and K/Na ratios, notably during dry periods. Groundwater salinity substantially decreased following severe flooding in 2011, notably in the lower catchment, confirming that flooding is an important mechanism for both recharge and maintaining groundwater quality. The integrated approach used in this study enabled effective interpretation of hydrological processes and can be applied to a variety of hydrological settings to synthesise and evaluate large hydrochemical datasets.

Geochemistry of water and ground water in the Nhecolandia, Pantanal of Mato Grosso, Brazil: Variability and associated processes

A distinctive feature of the Nhecolandia, a sub-region of the Pantanal wetland in Brazil, is the presence of both saline and freshwater lakes. Saline lakes used to be attributed to a past and phase during the Pleistocene. However, recent studies have shown that saline and fresh water lakes are linked by a continuous water table, indicating that saline water could come from a contemporary concentration process. This concentration process could also be responsible for the large chemical variability of the waters observed in the area. A regional water sampling has been conducted in surface and sub-surface water and the water table, and the results of the geochemical and statistical analysis are presented. Based on sodium contents, the concentration shows a 1: 4443 ratio. All the samples belong to the same chemical family and evolve in a sodic alkaline manner. Calcite or magnesian calcite precipitates very early in the process of concentration, probably followed by the precipitation of magnesian silicates. The most concentrated solutions remain under-saturated with respect to the sodium carbonate salt, even if this equilibrium is likely reached around the saline lakes. Apparently, significant amounts of sulfate and chloride are lost simultaneously from the solutions, and this cannot be explained solely by evaporative concentration. This could be attributed to the sorption on reduced minerals in a green sub-surface horizon in the "cordilhieira" areas. In the saline lakes, low potassium, phosphate, magnesium, and sulfate are attributed to algal blooms. Under the influence of evaporation, the concentration of solutions and associated chemical precipitations are identified as the main factors responsible for the geochemical variability in this environment (about 92 % of the variance). Therefore, the saline lakes of Nhecolandia have to be managed as landscape units in equilibrium with the present water flows and not inherited from a past and phase. In order to elaborate hydrochemical tracers for a quantitative estimation of water flows, three points have to be investigated more precisely: (1) the quantification of magnesium involved in the Mg-calcite precipitation; (2) the identification of the precise stoichiometry of the Mg-silicate; and (3) the verification of the loss of chloride and sulfate by sorption onto labile iron minerals.

High-frequency water quality monitoring in an urban catchment: hydrochemical dynamics, primary production and implications for the Water Framework Directive

This paper describes the hydrochemistry of a lowland, urbanised river-system, The Cut in England, using in situ sub-daily sampling. The Cut receives effluent discharges from four major sewage treatment works serving around 190,000 people. These discharges consist largely of treated water, originally abstracted from the River Thames and returned via the water supply network, substantially increasing the natural flow. The hourly water quality data were supplemented by weekly manual sampling with laboratory analysis to check the hourly data and measure further determinands. Mean phosphorus and nitrate concentrations were very high, breaching standards set by EU legislation. Though 56% of the catchment area is agricultural, the hydrochemical dynamics were significantly impacted by effluent discharges which accounted for approximately 50% of the annual P catchment input loads and, on average, 59% of river flow at the monitoring point. Diurnal dissolved oxygen data demonstrated high in-stream productivity. From a comparison of high frequency and conventional monitoring data, it is inferred that much of the primary production was dominated by benthic algae, largely diatoms. Despite the high productivity and nutrient concentrations, the river water did not become anoxic and major phytoplankton blooms were not observed. The strong diurnal and annual variation observed showed that assessments of water quality made under the Water Framework Directive (WFD) are sensitive to the time and season of sampling. It is recommended that specific sampling time windows be specified for each determinand, and that WFD targets should be applied in combination to help identify periods of greatest ecological risk. This article is protected by copyright. All rights reserved.

Uranium series disequilibria in ground waters from a fractured bedrock aquifer (Morungaba Granitoids-Southern Brazil): Implications to the hydrochemical behavior of dissolved U and Ra

Activity concentrations of dissolved U-234, U-238, Ra-226 and Ra-228 were determined in ground waters fromtwo deep wells drilled in Morungaba Granitoids (Southern Brazil). Sampling was done monthly for little longer than 1 year. Significant disequilibrium between U-238, U-234 and Ra-226 were observed in all samples. The variation of U-238 and U-234 activity concentrations and U-234/U-238 activity ratios is related to seasonal changes. Although the distance between the two wells is short (about 900m), systematic differences of activity concentrations of U isotopes, as well as of U-234/U-238, Ra-226/U-234 and Ra-228/Ra-226 activity ratios were noticed, indicating distinct host rock-water interactions. Slightly acidic ground water percolation through heterogeneous host rock, associated with different recharge processes, may explain uranium and radium isotope behavior. (c) 2008 Elsevier Ltd. All rights reserved.

An hydrochemical answer to a legislative demand involving health risk related to water quality

Effluents and surface waters around an area involved with the inking of tissues at Itatiba municipality, São Paulo State, Brazil, were chemically analyzed with the purpose of evaluating the influence on the water quality of the chemicals released, as well to provide answers to legislative requirements related to the São Paulo State Register 997 published on 31 May 1976.

Hydrochemical and stable isotopes (H, O, S) signatures in deep groundwaters of Parana basin, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Hydrochemical variability at the Upper Paraguay Basin and Pantanal wetland

Compartmentalization is a prerequisite to understand large wetlands that receive water from several sources. However, it faces the heterogeneity in space and time, resulting from physical, chemical and biological processes that are specific to wetlands. The Pantanal is a vast seasonally flooded continental wetland located in the centre of South America. The chemical composition of the waters that supply the Pantanal (70 rivers) has been studied in order to establish a compartmentalization of the wetland based on soil-water interactions. A PCA-based EMMA (End-Members Mixing Analysis) procedure shows that the chemistry of the rivers can be viewed as a mixture of 3 end-members, influenced by lithology and land use, and delimiting large regions. Although the chemical composition of the end-members changed between dry and wet seasons, their spatial distribution was maintained. The results were extended to the floodplain by simple tributary mixing calculation according to the hydrographical network and to the areas of influence for each river when in overflow conditions. The resulting map highlights areas of high geochemical contrast on either side of the river Cuiaba in the north, and of the rivers Aquidauana and Abobral in the south. The PCA-based treatment on a sampling conducted in the Nhecolandia, a large sub region of the Pantanal, allowed the identification and ordering of the processes that control the geochemical variability of the surface waters. Despite an enormous variability in electrical conductivity and pH, all data collected were in agreement with an evaporation process of the Taquari River water, which supplies the region. Evaporation and associated saline precipitations (Mg-calcite, Mg-silicates K-silicates) explained more than 77% of the total variability in the chemistry of the regional surface water sampling.