Groundwater quality on a waste disposal area due to sand mining activities in São Paulo state, Brazil

This investigation reports the results of a study realized in an area related to the development of sand mining activities, which belongs to Sibelco Mineração Ltd. The site is located around Analândia municipality, nearly in the center of São Paulo State, Brazil. Hydrochemical analyses of groundwater were realized under different periods of time, with the aim of evaluating the possibility of release of several constituents to the liquid phase, which may be a source of pollution of the surface hydrological resources and of the deeper Guarani aquifer. This is because the site is located at the recharge area of Guarani aquifer and some tributaries from Corumbataí river may also be suffering contamination, implying on the impoverishment of the water quality that are very important resources in the region, as they are extensively used for drinking purposes, among others.© 2011 WIT Press.

Hidroquímica e aspectos diagenéticos dos sistema aqüífero Bauru na região sudoeste do estado de São Paulo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo hidrogeoquímico da porção meridional do sistema aquífero Bauru no estado de São Paulo

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

Estudo hidrogeológico do aqüífero Tubarão na área de afloramento da porção central do Estado de São Paulo

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

Radioatividade e hidroquímica em águas subterrâneas do município de Botucatu (SP)

The main objective of this study is to determine the activity of Po-210, Pb-210 and gross alpha/beta radioactivity in groundwater collected in Botucatu, municipality of the São Paulo state, Brazil. Samples were collected in wells to perform the radiochemical analysis. Most wells are registered in DAEE, Sabesp or CPRM. The activity of polonium was obtained by the method of alpha spectrometry, held in LABIDRO at UNESP, Rio Claro. All samples showed radioactivity values below the maximum allowed by WHO, that are: gross alpha radioactivity = 0,5 Bq/L, gross beta radioactivity = 1,0 Bq/L, Po210 = 0,2 Bq/L and Pb210 = 0,1 Bq/L. The results of hydrochemical analysis were compared with the 1469 Ordinance of the Health Ministry, and all values are bellow the maximum allowed. The data also allowed obtain the samples classification using the Piper diagram. The samples AAB, Quinta do Manacás, Faz. Quatro Irmãs, Sesi, Sitio São José and ITE are classified as calcic bicarbonate; the samples Staroup and Caio are potassic; the samples Banespa and BTC are bicarbonate and mixed interms of dissolved cations; Sitio das Palmeiras sample is sodium bicarbonate; the sample Faz. São Paulo is chlorinated calcic; the sample Sítio Btu-Pardinho chlorinated and mixed interms of dissolved cations

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.

Three-dimensional geological modelling and multivariate statistical analysis of water chemistry data to analyse and visualise aquifer structure and groundwater composition in the Wairau Plain, Marlborough District, New Zealand

Concerns regarding groundwater contamination with nitrate and the long-term sustainability of groundwater resources have prompted the development of a multi-layered three dimensional (3D) geological model to characterise the aquifer geometry of the Wairau Plain, Marlborough District, New Zealand. The 3D geological model which consists of eight litho-stratigraphic units has been subsequently used to synthesise hydrogeological and hydrogeochemical data for different aquifers in an approach that aims to demonstrate how integration of water chemistry data within the physical framework of a 3D geological model can help to better understand and conceptualise groundwater systems in complex geological settings. Multivariate statistical techniques(e.g. Principal Component Analysis and Hierarchical Cluster Analysis) were applied to groundwater chemistry data to identify hydrochemical facies which are characteristic of distinct evolutionary pathways and a common hydrologic history of groundwaters. Principal Component Analysis on hydrochemical data demonstrated that natural water-rock interactions, redox potential and human agricultural impact are the key controls of groundwater quality in the Wairau Plain. Hierarchical Cluster Analysis revealed distinct hydrochemical water quality groups in the Wairau Plain groundwater system. Visualisation of the results of the multivariate statistical analyses and distribution of groundwater nitrate concentrations in the context of aquifer lithology highlighted the link between groundwater chemistry and the lithology of host aquifers. The methodology followed in this study can be applied in a variety of hydrogeological settings to synthesise geological, hydrogeological and hydrochemical data and present them in a format readily understood by a wide range of stakeholders. This enables a more efficient communication of the results of scientific studies to the wider community.

Sources of hydrochemical variability and implications associated with CSG water extraction

Coal Seam Gas (CSG) production is achieved by extracting groundwater to depressurize coal seam aquifers in order to promote methane gas desorption from coal micropores. CSG waters are characteristically alkaline, have a neutral pH (~7), are of the Na-HCO3-Cl type, and exhibit brackish salinity. In 2004, a CSG exploration company carried out a gas flow test in an exploration well located in Maramarua (Waikato Region, New Zealand). This resulted in 33 water samples exhibiting noteworthy chemical variations induced by pumping. This research identifies the main causes of hydrochemical variations in CSG water, makes recommendations to manage this effect, and discusses potential environmental implications. Hydrochemical variations were studied using Factor Analysis and this was supported with hydrochemical modelling and a laboratory experiment. This reveals carbon dioxide (CO2) degassing as the principal source of hydrochemical variability (about 33%). Factor Analysis also shows that major ion variations could also reflect changes in hydrochemical composition induced by different pumping regimes. Subsequent chloride, calcium, and TDS variations could be a consequence of analytical errors potentially committed during laboratory determinations. CSG water chemical variations due to degassing during pumping can be minimized with good completion and production techniques; variations due to sample degassing can be controlled by taking precautions during sampling, transit, storage and analysis. In addition, the degassing effect observed in CSG waters can lead to an underestimation of their potential environmental effect. Calcium precipitation due to exposure to normal atmospheric pressure results in a 23% increase in SAR values from Maramarua CSG water samples.

Linking three-dimensional geological modelling and multivariate statistical analysis to define groundwater chemistry baseline and identify inter-aquifer connectivity within the Clarence-Moreton Basin, Southeast Queensland, Australia

The Clarence-Moreton Basin (CMB) covers approximately 26000 km2 and is the only sub-basin of the Great Artesian Basin (GAB) in which there is flow to both the south-west and the east, although flow to the south-west is predominant. In many parts of the basin, including catchments of the Bremer, Logan and upper Condamine Rivers in southeast Queensland, the Walloon Coal Measures are under exploration for Coal Seam Gas (CSG). In order to assess spatial variations in groundwater flow and hydrochemistry at a basin-wide scale, a 3D hydrogeological model of the Queensland section of the CMB has been developed using GoCAD modelling software. Prior to any large-scale CSG extraction, it is essential to understand the existing hydrochemical character of the different aquifers and to establish any potential linkage. To effectively use the large amount of water chemistry data existing for assessment of hydrochemical evolution within the different lithostratigraphic units, multivariate statistical techniques were employed.

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.

Hydrostratigraphic and hydrochemical characterisation of aquifers, aquitards and coal seams in the Galilee and Eromanga basins, Central Queensland, Australia

Inter-aquifer mixing studies are usually made carrying out hydrochemical and isotopic techniques only. In this thesis these techniques have been integrated with three-dimensional geological modelling proving to be a better approach for inter—aquifer mixing assessment in regional areas, and also highlighting the influence of faulting in the understanding of groundwater and gas migration, which could not be possible using the two fist techniques alone. The results are of particular interest for coal seam gas basins and can even be used as exploration tools as areas of higher permeability and gas migration were identified.

Appraisal of groundwater resource in Holocene soil deposits by resistivity, hydrochemical and granulomerial studies in the Gulf of Mannar Coast from Southern India

This article is aimed to delineate groundwater sources in Holocene deposits area in the Gulf of Mannar Coast from Southern India. For this purpose 2-D electrical resistivity tomography (ERT), hydrochemical and granulomerical studies were carried out and integrated to identify hydrogeological structures and portable groundwater resource in shallow depths which in general appears in the coastal tracts. The 2-D ERT was used to determine the two-dimensional subsurface geological formations by multicore cable with Wenner array. Low resistivity of 1-5 Omega m for saline water appeared due to calcite at the depth of about 5 m below the ground level (bgl). Sea water intrusion was observed around the maximum resistivity as 5 Omega m at the 8 m depth, bgl in the calcite environs, but the calcareous sandstone layer shows around 15-64 Omega m at the 6 m depth, bgl. The hydrochemical variation of TDS, HCO3-, Cl-, Na+, K+, Ca2+, and Mg2+ concentrations was observed for the saline and sea water intrusion in the groundwater system. The granulometic analysis shows that the study area was under the sea between 5400 and 3000 year ago. The events of ice melting an unnatural ice-stone rain/hail among 5000-4000 years ago resulted in the inundation of sea over the area and deposits of late Holocene marine transgression formation up to Puthukottai quartzite region for a stretch of around 17 km.

A Factor analysis of hidrochemical composition of Llobregat river basin

Hydrogeological research usually includes some statistical studies devised to elucidate mean background state, characterise relationships among different hydrochemical parameters, and show the influence of human activities. These goals are achieved either by means of a statistical approach or by mixing models between end-members. Compositional data analysis has proved to be effective with the first approach, but there is no commonly accepted solution to the end-member problem in a compositional framework. We present here a possible solution based on factor analysis of compositions illustrated with a case study. We find two factors on the compositional bi-plot fitting two non-centered orthogonal axes to the most representative variables. Each one of these axes defines a subcomposition, grouping those variables that lay nearest to it. With each subcomposition a log-contrast is computed and rewritten as an equilibrium equation. These two factors can be interpreted as the isometric log-ratio coordinates (ilr) of three hidden components, that can be plotted in a ternary diagram. These hidden components might be interpreted as end-members. We have analysed 14 molarities in 31 sampling stations all along the Llobregat River and its tributaries, with a monthly measure during two years. We have obtained a bi-plot with a 57% of explained total variance, from which we have extracted two factors: factor G, reflecting geological background enhanced by potash mining; and factor A, essentially controlled by urban and/or farming wastewater. Graphical representation of these two factors allows us to identify three extreme samples, corresponding to pristine waters, potash mining influence and urban sewage influence. To confirm this, we have available analysis of diffused and widespread point sources identified in the area: springs, potash mining lixiviates, sewage, and fertilisers. Each one of these sources shows a clear link with one of the extreme samples, except fertilisers due to the heterogeneity of their composition. This approach is a useful tool to distinguish end-members, and characterise them, an issue generally difficult to solve. It is worth note that the end-member composition cannot be fully estimated but only characterised through log-ratio relationships among components. Moreover, the influence of each endmember in a given sample must be evaluated in relative terms of the other samples. These limitations are intrinsic to the relative nature of compositional data

An analysis of long-term trends, seasonality and short-term dynamics in water quality data from Plynlimon, Wales

This paper examines two hydrochemical time-series derived from stream samples taken in the Upper Hafren catchment, Plynlimon, Wales. One time-series comprises data collected at 7-hour intervals over 22 months (Neal et al., submitted, this issue), while the other is based on weekly sampling over 20 years. A subset of determinands: aluminium, calcium, chloride, conductivity, dissolved organic carbon, iron, nitrate, pH, silicon and sulphate are examined within a framework of non-stationary time-series analysis to identify determinand trends, seasonality and short-term dynamics. The results demonstrate that both long-term and high-frequency monitoring provide valuable and unique insights into the hydrochemistry of a catchment. The long-term data allowed analysis of long-termtrends, demonstrating continued increases in DOC concentrations accompanied by declining SO4 concentrations within the stream, and provided new insights into the changing amplitude and phase of the seasonality of the determinands such as DOC and Al. Additionally, these data proved invaluable for placing the short-term variability demonstrated within the high-frequency data within context. The 7-hour data highlighted complex diurnal cycles for NO3, Ca and Fe with cycles displaying changes in phase and amplitude on a seasonal basis. The high-frequency data also demonstrated the need to consider the impact that the time of sample collection can have on the summary statistics of the data and also that sampling during the hours of darkness provides additional hydrochemical information for determinands which exhibit pronounced diurnal variability. Moving forward, this research demonstrates the need for both long-term and high-frequency monitoring to facilitate a full and accurate understanding of catchment hydrochemical dynamics.

Does increased hydrochemical model complexity decrease robustness?

The aim of this study was, within a sensitivity analysis framework, to determine if additional model complexity gives a better capability to model the hydrology and nitrogen dynamics of a small Mediterranean forested catchment or if the additional parameters cause over-fitting. Three nitrogen-models of varying hydrological complexity were considered. For each model, general sensitivity analysis (GSA) and Generalized Likelihood Uncertainty Estimation (GLUE) were applied, each based on 100,000 Monte Carlo simulations. The results highlighted the most complex structure as the most appropriate, providing the best representation of the non-linear patterns observed in the flow and streamwater nitrate concentrations between 1999 and 2002. Its 5% and 95% GLUE bounds, obtained considering a multi-objective approach, provide the narrowest band for streamwater nitrogen, which suggests increased model robustness, though all models exhibit periods of inconsistent good and poor fits between simulated outcomes and observed data. The results confirm the importance of the riparian zone in controlling the short-term (daily) streamwater nitrogen dynamics in this catchment but not the overall flux of nitrogen from the catchment. It was also shown that as the complexity of a hydrological model increases over-parameterisation occurs, but the converse is true for a water quality model where additional process representation leads to additional acceptable model simulations. Water quality data help constrain the hydrological representation in process-based models. Increased complexity was justifiable for modelling river-system hydrochemistry. Increased complexity was justifiable for modelling river-system hydrochemistry.