Isotope tracing of submarine groundwater discharge offshore Ubatuba, Brazil: results of the IAEA-UNESCO SGD project

Results of groundwater and seawater analyses for radioactive ((3)H, (222)Rn, (223)Ra, (224)Ra, (226)Ra, and (228)Ra) and stable (D and (18)O) isotopes are presented together with in situ spatial mapping and time series (222)Rn measurements in seawater, direct seepage measurements using manual and automated seepage meters, pore water investigations using different tracers and piezometric techniques, and geoelectric surveys probing the coast. This study represents first time that such a new complex arsenal of radioactive and non-radioactive tracer techniques and geophysical methods have been used for simultaneous submarine groundwater discharge (SGD) investigations. Large fluctuations of SGD fluxes were observed at sites situated only a few meters apart (from 0cmd(-1) to 360cmd(-1); the unit represents cm(3)/cm(2)/day), as well as during a few hours (from 0cmd(-1) to 110cmd(-1)), strongly depending on the tidal fluctuations. The average SGD flux estimated from continuous (222)Rn measurements is 17+/-10cmd(-1). Integrated coastal SGD flux estimated for the Ubatuba coast using radium isotopes is about 7x10(3)m(3)d(-1) per km of the coast. The isotopic composition (deltaD and delta(18)O) of submarine waters was characterised by significant variability and heavy isotope enrichment, indicating that the contribution of groundwater in submarine waters varied from a small percentage to 20%. However, this contribution with increasing offshore distance became negligible. Automated seepage meters and time series measurements of (222)Rn activity concentration showed a negative correlation between the SGD rates and tidal stage. This is likely caused by sea level changes as tidal effects induce variations of hydraulic gradients. The geoelectric probing and piezometric measurements contributed to better understanding of the spatial distribution of different water masses present along the coast. The radium isotope data showed scattered distributions with offshore distance, which imply that seawater in a complex coast with many small bays and islands was influenced by local currents and groundwater/seawater mixing. This has also been confirmed by a relatively short residence time of 1-2 weeks for water within 25km offshore, as obtained by short-lived radium isotopes. The irregular distribution of SGD seen at Ubatuba is a characteristic of fractured rock aquifers, fed by coastal groundwater and recirculated seawater with small admixtures of groundwater, which is of potential environmental concern and has implications on the management of freshwater resources in the region.     

Isotope tracing of submarine groundwater discharge offshore Ubatuba, Brazil: results of the IAEA–UNESCO SGD project

Results of groundwater and seawater analyses for radioactive (³H, ²²²Rn, ²²³Ra, ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra) and stable (D and ¹⁸O) isotopes are presented together with in situ spatial mapping and time series ²²²Rn measurements in seawater, direct seepage measurements using manual and automated seepage meters, pore water investigations using different tracers and piezometric techniques, and geoelectric surveys probing the coast. This study represents first time that such a new complex arsenal of radioactive and non-radioactive tracer techniques and geophysical methods have been used for simultaneous submarine groundwater discharge (SGD) investigations. Large fluctuations of SGD fluxes were observed at sites situated only a few meters apart (from 0 cm d⁻¹ to 360 cm d⁻¹; the unit represents cm³/cm²/day), as well as during a few hours (from 0 cm d⁻¹ to 110 cm d⁻¹), strongly depending on the tidal fluctuations. The average SGD flux estimated from continuous ²²²Rn measurements is 17 ± 10 cm d⁻¹. Integrated coastal SGD flux estimated for the Ubatuba coast using radium isotopes is about 7 × 10³ m³ d⁻¹ per km of the coast. The isotopic composition (δD and δ¹⁸O) of submarine waters was characterised by significant variability and heavy isotope enrichment, indicating that the contribution of groundwater in submarine waters varied from a small percentage to 20%. However, this contribution with increasing offshore distance became negligible. Automated seepage meters and time series measurements of ²²²Rn activity concentration showed a negative correlation between the SGD rates and tidal stage. This is likely caused by sea level changes as tidal effects induce variations of hydraulic gradients. The geoelectric probing and piezometric measurements contributed to better understanding of the spatial distribution of different water masses present along the coast. The radium isotope data showed scattered distributions with offshore distance, which imply that seawater in a complex coast with many small bays and islands was influenced by local currents and groundwater/seawater mixing. This has also been confirmed by a relatively short residence time of 1–2 weeks for water within 25 km offshore, as obtained by short-lived radium isotopes. The irregular distribution of SGD seen at Ubatuba is a characteristic of fractured rock aquifers, fed by coastal groundwater and recirculated seawater with small admixtures of groundwater, which is of potential environmental concern and has implications on the management of freshwater resources in the region.     

Reconnaissance of submarine groundwater discharge at Ubatuba coast,Brazil, using 222Rn as a natural tracer

Submarine groundwater discharge (SGD), which includes fresh groundwater and recycled seawater, has been recognized as a widespread phenomenon that can provide important chemical elements to the ocean. Several studies have demonstrated that SGD may approach or even exceed freshwater sources in supplying nutrients to coastal zones. This work reports preliminary results of a study carried out in a series of small embayments of Ubatuba, S?o Paulo State, Brazil, covering latitudes between 23 degrees 26'S and 23 degrees 46'S and longitudes between 45 degrees 02'W and 45 degrees 11'W. The main aims of this research were to set up an analytical method to assess 222Rn and 226Ra activities in seawater samples and to apply the excess 222Rn inventories obtained to estimate SGD. Measurements made during the summer of 2001 included 222Rn and 226Ra in seawater, 226Ra in sediment, seawater and sediment physical properties, nutrients and seepage rates. A continuous 222Rn monitor was also used to determine in situ collection of data to study short-term changes at one location. All methods indicated significant inflow of subsurface fluids at rates in excess of several cm per day.     

Characterisation of heavy metal discharge into the Ria of Huelva

The Ria of Huelva estuary, in SW Spain, is known to be one of the most heavy metal contaminated estuaries in the world. River contribution to the estuary of dissolved Cu, Zn, Mn, Cr, Ni, Cd, and As were analysed for the period 1988-2001. The obtained mean values show that this contribution, both because of the magnitude of total metals (895.1 kg/h), composition, toxicity (8.7 kg/h of As+Cd+Pb) and persistence, is an incomparable case in heavy metal contamination of estuaries. The amount and typology of heavy metal discharge to the Ria of Huelva are related to freshwater flow (and, consequently, to rainfall); as a result, two different types of heavy metal discharge can be distinguished in the estuary: during low water (50% of the days), with only 19.3 kg/h of heavy metals, and during high water or flood (17% of the days), where daily maximum discharge of 72,475 kg of heavy metals were recorded, from which 1481 kg were of As, 470 kg of Pb, and 170 kg of Cd. In the most frequent situation (77% of the days), the Odiel River discharges from 90% to 100% of the freshwater received by the estuary. Despite this, the high concentration of heavy metals in the Tinto River water causes this river to discharge into the Ria of Huelva 12.5% of fluvial total dissolved metal load received by the estuary.     

Seasonal variation of air kerma rate in Sicily

Thermoluminescence dosimetry has been used to measure air kerma in 29 sites in Sicily. Four three month measurement campaigns have been carried out in order to assess seasonal variations. Average annual values between 20 and 90 nGy h(-1), after cosmic background subtraction, are reported. Average annual values are strongly dependent on site lithology, and we find that winter data are generally the highest, while spring and autumn rates are generally the lowest with very similar trends in any site. Summer values generally lay in between. Largest seasonal variations are found in sites along the southern coast of the island, probably because of stronger action of winds affecting radon, along with its progeny, concentrations at ground level.     

Coupled radon, methane and nitrate sensors for large-scale assessment of groundwater discharge and non-point source pollution to coastal waters

We constructed a survey system of radon/methane/nitrate/salinity to find sites of submarine groundwater discharge (SGD) and groundwater nitrate input. We deployed the system in Waquoit Bay and Boston Harbor, MA where we derived SGD rates using a mass balance of radon with methane serving as a fine resolution qualitative indicator of groundwater. In Waquoit Bay we identified several locations of enhanced groundwater discharge, out of which two (Childs and Quashnet Rivers) were studied in more detail. The Childs River was characterized by high nitrate input via groundwater discharge, while the Quashnet River SGD was notable but not a significant source of nitrate. Our radon survey of Boston Harbor revealed several sites with significant SGD, out of these Inner Harbor and parts of Dorchester Bay and Quincy Bay had groundwater fluxes accompanied by significant water column nitrogen concentrations. The survey system has proven effective in revealing areas of SGD and non-point source pollution.     

Using the useful: characteristics of used palms in south-eastern Ecuador

Plant families differ greatly with regard to their usefulness to humans. Within families there are also large differences in the usefulness between species; some are used for many different purposes, while most are used for few or no purposes. Which ones and to what extent species are used often varies between areas and cultural groups. To better understand variation in speciesȁ9 usefulness we studied the use of different palm species (Arecaceae) among two socio-cultural groups (one indigenous and one colonist group of mixed ethnic descent) living in the same area. We used regression and correlation analyses to determine to what degree use is related to ecological and morphological characteristics, to geographical differences in abundance, and to peopleȁ9s perceptions of speciesȁ9 availability. We found that abundance and height were the most important characteristics related to use, possibly due to the effect of height and abundance on salience, search time, and (for height) suitability for different purposes. Abundance was most important for palm heart extraction, probably due to the opportunistic nature of this activity. There was no difference between socio-cultural groups with regard to the relationship between palm abundance and use, but abundance seemed to be more decisive for people who used moderate amounts of palms. Finally, it was seen that peopleȁ9s estimates of palm abundance were not related to our measurements of abundance, which may be due to use of different spatial scales in evaluating abundance and to the subjective nature of terms such as “rare” and “abundant”.     

Present status of Rn in groundwater in Extremadura

Radon-222 was measured in groundwater sources of Extremadura (Spain), analyzing 350 samples from private and public springs, wells, and spas by liquid scintillation counting (LSC) and gamma spectrometry. The ²²²Rn activity concentrations ranged from 0.24 to 1168 Bq L⁻¹. The statistical analysis showed a log-normal distribution with a mean of (111 ± 7) Bq L⁻¹ and a median of (36 ± 3) Bq L⁻¹. A hydrogeological study revealed correlations between the activity concentration and the aquifer material's characteristics. A map of ²²²Rn in groundwater was elaborated and compared with the natural gamma radiation map for this region. About 35% of the samples showed ²²²Rn activity concentrations above the Euratom recommended limit of 100 Bq L⁻¹. Three uranium series radionuclides (²³⁸U, ²³⁴U, and ²²⁶Ra) were also assayed by alpha-particle spectrometry, estimating the annual effective dose due to the presence of these natural radionuclides in drinking water.     

Recent advances in the bioremediation of arsenic-contaminated groundwater

The biological treatment of groundwater is used primarily to remove electron donors from water sources, providing (biologically) stable drinking water, which preclude bacterial regrowth during subsequent water distribution. To the electron donors belong also the dissolved metal cations of ferrous iron and manganese, which are common contaminants found in most (anaerobic) groundwater. The removal of iron and manganese is usually accomplished by the application of chemical oxidation and filtration. However, biological oxidation has recently gained increased importance and application due to the existence of certain advantages, over the conventional physicochemical treatment. The oxidation of iron and manganese is accelerated by the presence of certain indigenous bacteria, the so-called "iron and manganese oxidizing bacteria." In the present paper, selected long-term experimental results will be presented, regarding the bioremediation of natural groundwater, containing elevated concentrations of iron and arsenic. Arsenic is considered as a primary pollutant in drinking water due to its high toxicity. Therefore, its efficient removal from natural waters intended for drinking water is considered of great importance. The application of biological processes for the oxidation and removal of dissolved iron was found to be an efficient treatment technique for the simultaneous removal of arsenic, from initial concentrations between 60 and 80 microg/l to residual (effluent) arsenic concentrations lower than the limit of 10 microg/l. The paper was focused on the removal of As(III) as the most common species in anaerobic groundwater and generally is removed less efficiently than the oxidized form of As(V). To obtain information for the mechanism of As(III) removal, X-ray photoelectron spectroscopy (XPS) analyses were applied and it was found that As(III) was partially oxidized to As(V), which enabled the high arsenic removal efficiency over a treatment period of 10 months.     

Common buzzards (Buteo buteo) bio-indicators of heavy metals pollution in Sicily (Italy)

The aim of this study was to evaluate the accumulation of toxic (As, Cd and Pb) and essential (Cu, Mn and Zn) metals in samples (feathers, liver, kidney, lung, intestine and muscle) of common buzzards (Buteo buteo) from Sicily, used as bio-indicators for monitoring environmental metals pollution. All samples of buzzards were collected at the “Recovery Center of Wild Fauna” of Palermo, through the Zooprophilactic Institute. The quantitative determinations of metals were carried out using an atomic absorbtion spectrophotometer (AAS). The results obtained showed the presence of metals in all samples analyzed. For toxic metals the highest levels of Pb and As were found in liver and those of Cd in kidney; for essential metals Zn levels were higher than Cu and Mn in all tissues analyzed. Significant differences are observed in metal levels between female and male and juvenile and adult bird samples.Highest metal levels found in liver, kidney and muscle can be considered indicative of chronic exposure to metals while the presence of metals in feathers can be consequential to storing and elimination processes. The results obtained suggest that common buzzards (Buteo buteo) may be very useful as bio-indicators for monitoring environmental pollution.     

Present status of 222Rn in groundwater in Extremadura

Radon-222 was measured in groundwater sources of Extremadura (Spain), analyzing 350 samples from private and public springs, wells, and spas by liquid scintillation counting (LSC) and gamma spectrometry. The (222)Rn activity concentrations ranged from 0.24 to 1168BqL(-1). The statistical analysis showed a log-normal distribution with a mean of (111+/-7)BqL(-1) and a median of (36+/-3)BqL(-1). A hydrogeological study revealed correlations between the activity concentration and the aquifer material's characteristics. A map of (222)Rn in groundwater was elaborated and compared with the natural gamma radiation map for this region. About 35% of the samples showed (222)Rn activity concentrations above the Euratom recommended limit of 100BqL(-1). Three uranium series radionuclides ((238)U, (234)U, and (226)Ra) were also assayed by alpha-particle spectrometry, estimating the annual effective dose due to the presence of these natural radionuclides in drinking water.     

Sorption behaviour of Am on marl groundwater colloids.

The sorption of americium on marl colloids is studied in a comprehensive way. In Na-HCO3 groundwater conditions, americium in the concentration range 3 x 10(-11)-3 x 10(10) M sorbs onto groundwater colloids. In these tests, the colloid concentration is rather high, i.e. Ccoll 1.7+/-1.3 mg l(-1) for sizes 505000 nm or Ncoll (1.7+/-0.1) x 10(11) l(-1) for sizes larger than 100 nm. These colloids are mainly chlorite and smectite/illite with an average size smaller than 500 nm. For the groundwater (pH 8.6, [Na+]-[HCO3]-2 x 10(-2) M), Kd values in the range 1-3 x 10(6)mlg(-1) are measured. These values are compared with experimental and modelled values reported earlier in the literature.     

Degradation of volatile chlorinated aliphatic priority pollutants in groundwater

The known degradation products and degradative pathways involving selected volatile aliphatic chlorinated hydrocarbons in soil-groundwater systems are summarized. Current data indicate that the most commonly found products of microbial degradation of these compounds come from reductive dehalogenation, while nonmicrobial degradations tend to involve hydrolysis and/or oxidation. However, conclusions must be regarded as tentative, since most of the available studies have involved model systems and extrapolations, rather than direct studies of compounds in groundwater systems. Other potentially complicating factors, such as mobility and volatilization, are mentioned. Current knowledge is discussed in the context of data that would be desirable to obtain in future studies.     

Conservation value of an exotic species: the case of coconuts on the Kayapo indigenous lands, south-eastern Amazonia

In a meeting between FUNAI (the Brazilian Indian National Foundation) and the Kayapo in the Kayapo village of Aukre, in October 2005, the Kayapo Indians requested support to increase the culture of coconuts (Cocos nucifera) in their lands. The introduction of exotic species is a cause of biological diversity loss throughout the world. However, this is by no means applicable to all kinds of exotic species. We argue that the culture of coconuts may actually be a useful tool for the conservation of this country’s indigenous lands, despite criticism to the contrary. It may also be useful as source for raw material for the indigenous people who are presently experiencing a population boom. For the Kayapo of south-eastern Amazonia, such a demographic explosion, coupled with their increasing dependence on money to purchase industrialized goods, tend to substantially increase the pressure on their lands, which still contain a substantial amount of well-preserved seasonally-dry Amazonian forests. We investigated the actual economic relevance of coconuts for the Kayapo by measuring human and coconut populations and found that this exotic palm is not important for the subsistence of these Indians, due to coconut scarcity, and that such importance is not forthcoming. In the Amazon, coconuts may be particularly useful for the Indians’ nutrition due to the high energetic value of the solid endosperm of the mature fruit. Therefore, given the importance of indigenous lands for the conservation of the Amazonian forests, the encouragement of subsistence coconut cultures in indigenous lands is defensible as a measure for the conservation of biodiversity.     

Soil transport and plant uptake of radio-iodine from near-surface groundwater

This paper describes a 12-month experiment designed to study the extent of upward migration of (125)I (as a surrogate for (129)I) from near-surface groundwater, through a 50-cm column of soil and into perennial ryegrass. The water table was established at a depth of 45 cm below the soil surface. By 3 months, (125)I had migrated about half way up the soil column. After this, it tended to accumulate just above this mid-point, with only very small amounts being transported to the upper 20 cm of soil. This behaviour seemed to be explained well by soil moisture and redox conditions. The experiment indicated that (125)I was mobile only within the saturated/low redox zone at the base of the soil column and accumulated in the zone of transition between anoxic and oxic soil conditions. Uptake of (125)I by the ryegrass was found to be low.     

Evaluation of groundwater contamination and its impact: an interdisciplinary approach

The study aimed at determining the socio-economic issues due to municipal solid waste dumping, the extent of groundwater contamination and the groundwater dependency around Perungudi dumpsite in Tamil Nadu, India. Sampling and analysis of groundwater and leachate show the contamination migration is due to dumpsite leachate. The concentrations of contaminants were more severe within 1.5?km along groundwater flow direction mainly due to the geological profile. The Piper diagram also shows that the groundwater sampled within 3?km in the flow direction was classified as Na–Cl type. Studies conducted within contaminated areas to determine the groundwater usage showed that higher percentage of lower and middle socio-economic status categories was using the groundwater for domestic purposes, which may lead to health issues. The present study suggests that proper solid waste management and groundwater remediation techniques along with the people’s involvement are necessary to reduce the consequences of groundwater contamination on the people residing around the dumpsite.     

Characterisation of human exposure pathways to perfluorinated compounds--comparing exposure estimates with biomarkers of exposure

Commercially used per- and polyfluorinated compounds (PFCs) have been widely detected in humans, but the sources of human exposure are not fully characterized. The objectives of this study were to assess the relative importance of different exposure pathways of PFCs in a group of Norwegians and compare estimated intakes with internal doses obtained through biomonitoring. Individual PFC intakes from multiple exposure sources for a study group of 41 Norwegian women were estimated using measured PFC concentrations in indoor air and house dust as well as information from food frequency questionnaires and PFC concentrations in Norwegian food. Food was generally the major exposure source, representing 67-84% of the median total intake for PFOA and 88-99% for PFOS using different dust ingestion rates and biotransformation factors of 'precursor' compounds. However, on an individual basis, the indoor environment accounted for up to around 50% of the total intake for several women. Significant positive associations between concentrations of PFCs in house dust and the corresponding serum concentrations underline the importance of indoor environment as an exposure pathway for PFCs. For breast-fed infants, breast milk was calculated to be the single most important source to PFCs by far. The estimated intakes were confirmed by comparing serum concentrations of PFOA and PFOS calculated using PK models, with the corresponding concentrations measured in serum. Even though food in general is the major source of exposure for PFCs, the indoor environment may be an important contributor to human exposure. This study provides valuable knowledge for risk assessment of PFCs and control strategies.     

Assessment of groundwater potential in Tirukalukundram block of southern Chennai Metropolitan Area

Groundwater is an important resource in all major urban centres. Continuous extraction leads to degradation and depletion in the water quality which can be protected by selecting proper groundwater recharging techniques. The present study aims to determine the groundwater potential by integrating the remote sensing and geographic information system which helps to identify the locations which are in critical stage and immediate steps can be taken to recharge the groundwater. Thirukalukundram block of Kanchipuram district in Tami Nadu, India, has been chosen as study area. To demarcate the groundwater potential zone, surface attributes such as geomorphology, land use/land cover, contour map, drainage density and sub-surface attributes such as lineaments and soil maps are created using satellite imageries, toposheet, soil and geomorphology data of the study area. The thematic maps prepared using geographic information system and weights have been assigned to the attributes by considering the influence on the storage capacity of groundwater. Four categories of groundwater potential zones such as below low, low, moderate and high have been classified. From the analysis, 5% along the coastal plain area covers high groundwater potential zone, 20% of the area towards north-west and south-west hold moderate groundwater potential. 60% of the total area hold low groundwater potential zone which are located towards south-west direction. 15% of the study area contains below low groundwater potential zone in parts of south-west direction. This study helps to identify the suitable locations for extraction and recharge of groundwater.     

Vulnerability of human environment to risk: case of groundwater contamination risk

Based on a theoretical revision of the social vulnerability concept, this article proposes a scheme of vulnerability indicators within the human environment focused on different aetiology risks. An adaptation of this generic scheme of vulnerability factors is set for the specific field of aquifer contamination risk, as well as a methodology for its analysis. Finally, model application examples are given for the Sierra de Líbar and Sierra de Mijas carbonate aquifers and the Vélez River detrital aquifer, all of which are located in the south of Spain. Obtained cartography results show a range of utilities for risk mitigation and permit appropriate spatial discrimination for its performance over different scales. The exposure and vulnerability of the groundwater contamination risk concept is evaluated in specific maps, taking into account the resident population as well as their assets.     

The challenge of groundwater governance: case studies from Spain and Australia

This paper examines the relevance to groundwater management of Ostrom’s design principles for managing common property resources. Experience in four case studies of groundwater management in the Murray Darling Basin in Australia and the Upper Guadiana Basin in Spain suggests that while Ostrom’s design principles are relevant, sustainable groundwater management depends on the effective collaboration between government authorities and water users. A flexible and adaptive management approach is required, with collaboration between scientists, policy makers, water suppliers, and water users. Key management challenges include agreeing on a sustainable level of extraction, and establishing effective coordination and collaboration, and monitoring and control systems. Further case studies of groundwater management and their synthesis could make a useful contribution to the transition towards sustainable groundwater management regimes.