Nutrient-rich submarine groundwater discharge fuels the largest green tide in the world.

One of the largest "green tide" (Ulva prolifera) outbreaks in the world has occurred every year from 2007 to present in the Southern Yellow Sea, China. Currently, the coastal area around Jiangsu Province (Subei Shoal region) is thought to be the origination point of these giant green tide blooms. The combination of high nutrient demand but low river discharge and other inputs suggests that there is a significant flux of submarine groundwater discharge (SGD) in this area. By using a radium mass balance model, we estimated the SGD flux in the area to be (0.7-1.4) × 109 m3 d-1 (6.1-12 cm d-1), at the high end of SGD fluxes worldwide. Geographically, Subei Shoal is less than 5% of the entire Southern Yellow Sea area, while our calculated SGD flux just for the shoal area is ~3 times larger than previously documented for the whole Southern Yellow Sea. Therefore, Subei Shoal may be considered a SGD hotspot that plays an important role in SGD associated material fluxes. Compared to inputs from local rivers, atmospheric deposition, and anthropogenic activities, SGD-derived nutrients are the main source term that can support the growth of macroalgae. We specifically highlight that this type of areas that are shallow, intensively mixed, anthropogenically polluted, sandy or muddy with heavy bio-irrigation, may have a higher risk of suffering harmful ecological problems, even with limited terrestrial runoff.

A rapid and inexpensive method for 226Ra and 228Ra measurements of high TDS groundwaters.

A series of laboratory-scale studies was conducted by preconcentrating (226)Ra from spiked water test samples using Purolite ion-exchange resin to evaluate the adsorption efficiency of the resin under varying conditions. After removing the resin from the columns, it was sealed in gas-tight containers and measured via gamma spectrometry. The Purolite resin showed high radium uptake and retention from natural waters in the presence of high iron and total dissolved solids (TDS). This procedure allowed us to process a large number of high TDS samples at a typical rate of 15 samples/day using three germanium detectors. Quality assurance and method validation have been achieved by analyzing selected groundwater samples, with different (226)Ra activities and high TDS values, and comparing the results to those using alpha spectrometry with a (133)Ba yield tracer. There was very good agreement between the obtained (226)Ra activities by both methods.

Isotopic, geophysical and biogeochemical investigation of submarine groundwater discharge: IAEA-UNESCO intercomparison exercise at Mauritius Island.

Submarine groundwater discharge (SGD) into a shallow lagoon on the west coast of Mauritius Island (Flic-en-Flac) was investigated using radioactive ((3)H, (222)Rn, (223)Ra, (224)Ra, (226)Ra, (228)Ra) and stable ((2)H, (18)O) isotopes and nutrients. SGD intercomparison exercises were carried out to validate the various approaches used to measure SGD including radium and radon measurements, seepage rate measurements using manual and automated meters, sediment bulk conductivity and salinity surveys. SGD measurements using benthic chambers placed on the floor of the Flic-en-Flac Lagoon showed discharge rates up to 500 cm/day. Large variability in SGD was observed over distances of a few meters, which were attributed to different geomorphological features. Deployments of automated seepage meters captured the spatial and temporal variability of SGD with a mean seepage rate of 10 cm/day. The stable isotopic composition of submarine waters was characterized by significant variability and heavy isotope enrichment and was used to predict the contribution of fresh terrestrially derived groundwater to SGD (range from a few % to almost 100%). The integrated SGD flux, estimated from seepage meters placed parallel to the shoreline, was 35 m(3)/m day, which was in reasonable agreement with results obtained from a hydrologic water balance calculation (26 m(3)/m day). SGD calculated from the radon inventory method using in situ radon measurements were between 5 and 56 m(3)/m per day. Low concentrations of radium isotopes observed in the lagoon water reflected the low abundance of U and Th in the basalt that makes up the island. High SGD rates contribute to high nutrients loading to the lagoon, potentially leading to eutrophication. Each of the applied methods yielded unique information about the character and magnitude of SGD. The results of the intercomparison studies have resulted a better understanding of groundwater-seawater interactions in coastal regions. Such information is an important pre-requisite for the protection and management of coastal freshwater resources.

Experience in using radon and thoron data to solve environmental and water problems.

This study aims to introduce thoron ((220)Rn), a naturally occurring isotope, as a new groundwater tracer for detecting groundwater seepage into Bangkok canals. Previous studies by the group using radioactive radon ((222)Rn) and conductivity as groundwater tracers suggested that there is shallow groundwater seeping into the man-made canals ('klongs') around Bangkok. Furthermore, the groundwater was shown to be an important pathway of nutrient contamination to the surface waters. Thoron is a member of the natural (232)Th decay chain, has exactly the same chemical properties as radon, but has a much shorter half-life (56 s) than radon (3.84 d). By using its advantage of rapid decay, if one detects thoron in the environment, there must be a source nearby. Thus, thoron is potentially an excellent prospecting tool. In the case of measurements in natural waters, sources of thoron should indicate the point of groundwater discharges more precisely than radon. During the surveys in the canals of Bangkok, thoron was successfully measured and its distribution was more variable than that of radon, suggesting that seepage into the canals is not uniform.

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 7x10(3) m3 d(-1) per km of the coast. The isotopic composition (deltaD and delta18O) 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.

Automated measurement of 224Ra and 226Ra in water.

We present a new simple approach for automated, non-destructive measurement of the alpha-emitting radium isotopes ((223)Ra, (224)Ra, and (226)Ra) in water based on the emanation of their respective radon daughters ((219)Rn, (220)Rn, and (222)Rn). The method combines the high adsorption uptake of MnO(2) Resin for radium (K(d)=2.4 x 10(4)ml/g) over a wide pH range with the simplicity of the activity registration using a commercial radon-in-air analyzer (RAD7, DURRIDGE Company, Inc). Radium is first adsorbed onto the MnO(2) Resin by passing a water sample through the resin packed in a gas-tight glass cartridge. The same cartridge is then connected to the radon analyzer via a simple tubing system to circulate air through the resin and a drying system. The efficiency of the proposed system is determined by running standards prepared in the same manner. Our results indicate that the efficiency for (226)Ra is >22% if both (218)Po and (214)Po counts are collected. This is comparable with typical efficiencies for alpha spectrometry but with much less sample preparation. We estimate that an MDA of 0.8 pCi/L for (226)Ra may be obtained with this new approach using a 1L water sample and less than 4h of counting.

Quantifying submarine groundwater discharge in the coastal zone via multiple methods.

Submarine groundwater discharge (SGD) is now recognized as an important pathway between land and sea. As such, this flow may contribute to the biogeochemical and other marine budgets of near-shore waters. These discharges typically display significant spatial and temporal variability making assessments difficult. Groundwater seepage is patchy, diffuse, temporally variable, and may involve multiple aquifers. Thus, the measurement of its magnitude and associated chemical fluxes is a challenging enterprise. A joint project of UNESCO and the International Atomic Energy Agency (IAEA) has examined several methods of SGD assessment and carried out a series of five intercomparison experiments in different hydrogeologic environments (coastal plain, karst, glacial till, fractured crystalline rock, and volcanic terrains). This report reviews the scientific and management significance of SGD, measurement approaches, and the results of the intercomparison experiments. We conclude that while the process is essentially ubiquitous in coastal areas, the assessment of its magnitude at any one location is subject to enough variability that measurements should be made by a variety of techniques and over large enough spatial and temporal scales to capture the majority of these changing conditions. We feel that all the measurement techniques described here are valid although they each have their own advantages and disadvantages. It is recommended that multiple approaches be applied whenever possible. In addition, a continuing effort is required in order to capture long-period tidal fluctuations, storm effects, and seasonal variations.

Characterisation of submarine groundwater discharge offshore south-eastern Sicily.

A complex approach in characterisation of submarine groundwater discharge (SGD) off south-eastern Sicily comprising applications of radioactive and non-radioactive tracers, direct seepage measurements, geophysical surveys and a numerical modelling is presented. SGD fluxes in the Donnalucata boat basin were estimated by direct seepage measurements to be from 4 to 12Ls(-1), which are comparable with the total SGD flux in the basin of 17Ls(-1) obtained from radon measurements. The integrated SGD flux over the Donnalucata coast estimated on the basis of Ra isotopes was around 60m(3)s(-1) per km of the coast. Spatial variations of SGD were observed in the Donnalucata boat basin, the average (222)Rn activity concentration in seawater varied from approximately 0.1kBqm(-3) to 3.7kBqm(-3) showing an inverse relationship with salinity. The continuous monitoring carried out at the site closest to the coast has revealed an inverse relationship of (222)Rn activity concentration on the tide. The (222)Rn concentrations in seawater varied from 2.3kBqm(-3) during high tides to 4.8kBqm(-3) during low tides, thus confirming an influence of the tide on submarine groundwater discharge. Stable isotopes (delta(2)H and delta(18)O) showed that SGD samples consist up to 50% of groundwater. Geo-electrical measurements showed a spatial variability of the salt/fresh water interface and its complex transformation in the coastal zone. The presented results imply that in the studied Donnalucata site there are at least two different sources of SGD, one superficial, represented by mixed fresh water and seawater, and the second one which originates in a deeper limestone aquifer.

Radium-228 determination of natural waters via concentration on manganese dioxide and separation using Diphonix ion exchange resin.

The objective of this work was to establish a new procedure for 228Ra determination of natural waters via preconcentration of radium on MnO2 and separation of its daughter, 228Ac, using Diphonix ion exchange resin. Following removal of potential interferences via passage through an initial Diphonix Resin column, the first daughter of 228Ra, 228Ac, is isolated by chromatographic separation via a second Diphonix column. A holding time of > 30 h for 228Ac ingrowth in between the two column separations ensures secular equilibrium. Barium-133 is used as a yield tracer. Actinium-228 is eluted from the second Diphonix Resin with 5 ml 1M 1-Hydroxyethane-1,1-diphosphonic acid (HEDPA) and quantified by addition of scintillation cocktail and LSC counting. Radium (and 133Ba) from the load and rinse solutions from the 2nd Diphonix column may be prepared for alpha spectrometry (for determination of 223Ra, 224Ra, and 226Ra) by BaSO4 microprecipitation and filtration. Decontamination tests indicate that U, Th, and Ra series nuclides do not interfere with these measurements, although high contents of 90Sr (90Y) require additional treatment for accurate measurement of 228Ra. Addition of stable Sr as a "hold back" carrier during the initial MnO2 preconcentration step was shown to remove most 90Sr interference.

Preconcentration of radium isotopes from natural waters using MnO2 Resin.

We have characterized "MnO2 Resin," a new resin developed by the PG Research Foundation, for radium adsorption over wide ranges of pH, reaction times and salt concentrations. We show that the sorption of 133Ba (used as a proxy for Ra) is highly dependent on pH with the most useful range from pH 4 to 8. The surface layers of the Mn oxides apparently become more positively charged under acidic conditions (below pH 4), which prevents diffusion of positively charged alkaline earth species (e.g. Ba2+, Ra2+) into the sorption sites. Adsorption at higher pH is thought to be inhibited because of carbonate complexation. We found that the sorption characteristics for radium onto MnO2 Resin are especially favorable for low-salinity waters but the sorption is still very satisfactory for highly salted solutions (KD=2.8x10(4) in both cases) but with slower kinetics. For analytical purposes, both column and pump experiments showed high recoveries with no measurable discrimination between Ra and Ba regardless of flow rates in fresh water. Seawater tests showed that recoveries of Ra and Ba are lower than fresh water at elevated flow rates with Ra adsorption higher than Ba at flow rates above 10 ml/min.

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, São 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.

Nuclide migration and the environmental radiochemistry of Florida phosphogypsum.

Phosphogypsum, a waste by-product derived from the wet process production of phosphoric acid, represents one of the most serious problems facing the phosphate industry in Florida today. This by-product gypsum precipitates during the reaction of sulfuric acid with phosphate rock and is stored at a rate of about 40 million tons per year on several stacks in central and northern Florida. The main problem associated with this material concerns the relatively high levels of natural uranium-series radionuclides and other impurities which could have an impact on the environment and prevent its commercial use. We have studied the potential release of radionuclides from phosphogypsum by: (i) analysis of stack fluids, groundwaters, and soils associated with gypsum stacks; and (ii) geochemical modeling. Stack fluids were observed to be very high in dissolved uranium and 210Pb with only moderate concentrations of 226Ra. Underlying soils tend to be enriched in U and 210Pb indicating precipitation when acidic stack fluids enter a buffered environment. Modeling results showed significant increases in radionuclide complexes with sulfate and phosphate, resulting in relatively mobile uncharged or negatively charged solution species within the stacks with likely precipitation of multicomponent solids with increasing pH below the stack. Our evidence thus suggests that, while phosphogypsum stacks do contain significant quantities of dissolved radionuclides, removal mechanisms appear to prevent large-scale migration of radionuclides to the underlying aquifer.

Measurement of 224Ra and 225Ra activities in natural waters using a radon-in-air monitor.

We report a simple new technique for measuring low-level radium isotopes (224Ra and 226Ra) in natural waters. The radium present in natural waters is first preconcentrated onto MnO2-coated acrylic fiber (Mn fiber) in a column mode. The radon produced from the adsorbed radium is then circulated through a closed air-loop connected to a commercial radon-in-air monitor. The monitor counts alpha decays of radon daughters (polonium isotopes) which are electrostatically collected onto a silicon semiconductor detector. Count data are collected in energy-specific windows, which eliminate interference and maintain very low backgrounds. Radium-224 is measured immediately after sampling via 220Rn (216Po), and 226Ra is measured via 222Rn 218Po) after a few days of ingrowth of 222Rn. This technique is rapid, simple, and accurate for measurements of low-level 224Ra and 226Ra activities without requiring any wet chemistry. Rapid measurements of short-lived 222Rn and 224Ra, along with long-lived 226Ra, may thus be made in natural waters using a single portable system for environmental monitoring of radioactivity as well as tracing of various geochemical and geophysical processes. The technique could be especially useful for the on-site rapid determination of 224Ra which has recently been found to occur at elevated activities in some groundwater wells.

Optimizing the removal of carbon phases in soils and sediments for sequential chemical extractions by coulometry.

We have developed a coulometric technique to optimize the removal of the carbonate and organic fractions for sequential chemical extractions of soils and sediments. The coulometric system facilitates optimizing these two fractions by direct real-time measurement of carbon dioxide (CO2) evolved during the removal of these two fractions. Further analyses by ICP-MS and alpha-spectrometry aided in interpreting the results of coulometry experiments. The effects of time, temperature, ionic strength and pH were investigated. The sensitivity of the coulometric reaction vessel/detection system was sufficient even at very low total carbon content (< 0.1 mol kg-1). The efficiency of the system is estimated to be 96% with a standard deviation of 8%. Experiments were carried out using NIST Standard Reference Materials 4357 Ocean Sediment (OS), 2704 Buffalo River Sediment (BRS), and pure calcium carbonate. Carbonate minerals were dissolved selectively using an ammonium acetate-acetic acid buffer. Organic matter was then oxidized to CO2 using hydrogen peroxide (H2O2) in nitric acid. The carbonate fraction was completely dissolved within 120 min under all conditions examined (literature suggests up to 8 h). For the OS standard, the oxidation of organic matter self-perpetuates between 45 and 50 degrees C, a factor of two less than commonly suggested, while organic carbon in the BRS standard required 80 degrees C for the reaction to proceed to completion. For complete oxidation of organic matter, we find that at least three additions of H2O2 are required (popular methods suggest one or two).

Holocene mean uplift rates across an active plate-collision boundary in taiwan.

Samples of Holocene fossil coral from uplifted reefs of three tectonically distinct, yet geographically proximal regions of Taiwan have been dated by uranium-series and (14)C isotopes. Applying corrections for altitude change caused by sea level fluctuations enables evaluation of long-term average Holocene uplift rates for three areas across an active convergent margin: (i) the Hengchun Peninsula of the Eurasian tectonic plate; (ii) the Eastern Coastal Range of Taiwan, a plate boundary; and (iii) two offshore islands, Lanyu and Lutao, both situated on the leading edge of the adjoining Philippine Plate. The data indicate that while all three areas have experienced uplift through the Holocene, plate collision has caused significantly higher uplift rates in the region directly along the plate boundary.

Determination of (210)Pb, (210)Bi and (210)Po in natural waters and other materials by electrochemical separation.

An improved method for determination of (210)Pb, (210)Bi and (210)Po in both natural waters and solid materials has been developed. Polonium-210 is spontaneously plated onto a silver disc from dilute hydrochloric acid medium. Bismuth-210 is then electro-deposited onto a platinum gauze cathode directly from the same solution, with a graphite rod as anode. Finally, (210)Pb is electro-deposited from a fluoroborate medium onto the same platinum gauze, used as the anode. All three nuclides are subsequently measured by standard low-level alpha and beta counting techniques. The speed of this method (approximately 6 hr per sample after pretreatment) is a distinct advantage over existing techniques, as (210)Bi must be quickly separated from (210)Pb because of its 5.02-day half-life. Another advantage of this method is that the chemical form of the sample solution is suitable for use of established separation schemes for determining other decay-series isotopes (U, Th, Pa, etc.) after the three short-lived nuclides have been processed.

Growth rates of phosphate nodules from the continental margin off peru.

Modern sea-floor phosphorite nodules sampled from off the coast of Peru are shown to grow at rates of millimeters per thousand years in spite of the fact that the measured accumulation rates of the underlying sediment are two to four orders of magnitude faster. Phosphate nodules grow downward into soft sediment, and the rates of phosphorus accumulation into nodules are approximately equal to the upward diffusive flux of dissolved phosphate inferred from pore water profiles. These results demonstrate that phosphorus in nodules originates from regeneration in sediments rather than as a result of direct precipitation from bottom waters.

Contemporary phosphorites on the continental margin of peru.

Phosphorite nodules occurring along the biologically productive continental margin of Peru have been dated by uranium-series methods. The radiometric ages range from late Pleistocene to Recent, indicating that phosphorities are currently forming in this area.