Geochemical and isotopic constraints on groundwater-surface water interactions in a highly anthropized site. The Wolfen/Bitterfeld megasite (Mulde subcatchment, Germany)

The Bitterfeld/Wolfen region is a megasite with multiple contaminant sources from more than a century of industrial activity, which have a considerable impact on the environment. At present, the contaminated groundwater covers an area of about 25km(2) and poses a threat for the surrounding aquifers and the Mulde River. This study focuses on the Schachtgraben, a man-made channel in the Mulde Floodplain that collects the effluents of the industrial area. It aims to characterise the relationship between surface water (channels, rivers) and the groundwater in the shallow Quaternary aquifer. Waters are Ca-SO(4) type with TDS reaching 3.8gL(-1) in the industrial area. Stable isotopes (delta(18)O, delta(2)H) show that two of the rivers are recharged mainly by groundwater that can be divided into two groups. Strontium isotopes ((87)Sr/(86)Sr) designate different geochemical end-members and enable the identification of mixing between natural and anthropogenic surface and groundwater.     

Metals in bulk deposition and surface waters at two upland locations in northern England

Concentrations of aluminium and minor metals (Mn, Ni, Cu, Zn, Sr, Cd, Ba, Pb) were measured in precipitation and surface water at two upland locations (Upper Duddon Valley, UDV; Great Dun Fell, GDF) in northern England for 1 year commencing April 1998. At both locations, the loads in bulk precipitation were at the lower ends of ranges reported for other rural and remote sites, for the period 1985-1995. The deposited metals were mostly in the dissolved form, and their concentrations tended to be greatest when rainfall volumes were low. The concentrations of Cu, Zn and Pb in deposition were correlated (r2 > or = 0.40) with concentrations of non-marine sulphate. Three streams, ranging in mean pH from 5.07 to 7.07, and with mean concentrations of dissolved organic carbon (DOC) < 1 mg l(-1). were monitored at UDV, and two pools (mean pH 4.89 and 6.83, mean DOC 22 and 15 mg l(-1)) at GDF. Aluminium and the minor metals were mainly in the dissolved form, and in the following ranges (means of 49-51 samples. microg l(-1)): Al 36-530. Mn 4.4-36, Ni 0.26-2.8, Cu 0.25-1.7, Zn 2.1-30, Cd 0.03-0.16, Ba 1.9-140, Pb 0.10-4.5. Concentrations were generally higher at GDF. Differences in metal concentrations between the two locations and between waters at each location, and temporal variations in individual waters, can be explained qualitatively in terms of sorption to solid-phase soil organic matter and mineral surfaces, complexation and transport by DOC, and chemical weathering. The UDV catchments are sinks for Pb and sources of Al, Mn, Sr, Cd and Ba. The GDF catchments are sources of Al, Mn, Ni, Zn, Sr, Cd and Ba. Other metals measured at the two locations are approximately in balance. Comparison of metal:silicon ratios in the surface waters with values for silicate rocks indicates enrichment of Ni and Cu, and substantial enrichment of Zn, Cd and Pb. These enrichments, together with high metal deposition in the past, make it likely that concentrations of the metals in the surface waters are governed by release from catchment pools of atmospherically-deposited metal. The catchments appear to be responding on a time scale of decades, possibly centuries, to changes in metal deposition. For the more acid waters at UDV, the calculated free-ion concentrations of Al are similar to published LC50 values for acute toxicity towards fish. The free-ion concentrations of Ni, Cu, Zn and Cd in all the surface waters are one-to-four orders of magnitude lower than reported LC50 values for fish.     

Amazon River dissolved load: temporal dynamics and annual budget from the Andes to the ocean

The aim of the present study is to estimate the export fluxes of major dissolved species at the scale of the Amazon basin, to identify the main parameters controlling their spatial distribution and to identify the role of discharge variability in the variability of the total dissolved solid (TDS) flux through the hydrological cycle. Data are compiled from the monthly hydrochemistry and daily discharge database of the “Programa Climatologico y Hidrologico de la Cuenca Amazonica de Bolivia” (PHICAB) and the HYBAM observatories from 34 stations distributed over the Amazon basin (for the 1983–1992 and 2000–2012 periods, respectively). This paper consists of a first global observation of the fluxes and temporal dynamics of each geomorphological domain of the Amazon basin. Based on mean interannual monthly flux calculations, we estimated that the Amazon basin delivered approximately 272?×?10⁶ t year^?1 (263–278) of TDS during the 2003–2012 period, which represents approximately 7 % of the continental inputs to the oceans. This flux is mainly made up by HCO₃, Ca and SiO₂, reflecting the preferential contributions of carbonate and silicate chemical weathering to the Amazon River Basin. The main tributaries contributing to the TDS flux are the Marañon and Ucayali Rivers (approximately 50 % of the TDS production over 14 % of the Amazon basin area) due to the weathering of carbonates and evaporites drained by their Andean tributaries. An Andes–sedimentary area–shield TDS flux (and specific flux) gradient is observed throughout the basin and is first explained by the TDS concentration contrast between these domains, rather than variability in runoff. This observation highlights that, under tropical context, the weathering flux repartition is primarily controlled by the geomorphological/geological setting and confirms that sedimentary areas are currently active in terms of the production of dissolved load. The log relationships of concentration vs discharge have been characterized over all the studied stations and for all elements. The analysis of the slope of the relationship within the selected contexts reveals that the variability in TDS flux is mainly controlled by the discharge variability throughout the hydrological year. At the outlet of the basin, a clockwise hysteresis is observed for TDS concentration and is mainly controlled by Ca and HCO₃ hysteresis, highlighting the need for a sampling strategy with a monthly frequency to accurately determine the TDS fluxes of the basin. The evaporite dissolution flux tends to be constant, whereas dissolved load fluxes released from other sources (silicate weathering, carbonate weathering, biological and/or atmospheric inputs) are mainly driven by variability in discharge. These results suggest that past and further climate variability had or will have a direct impact on the variability of dissolved fluxes in the Amazon. Further studies need to be performed to better understand the processes controlling the dynamics of weathering fluxes and their applicability to present-day concentration–discharge relationships at longer timescales.     

The chemical and strontium isotope composition of atmospheric aerosols over Japan: the contribution of long-range-transported Asian dust (Kosa)

Atmospheric aerosols have been collected at four sites around Japan during 2000. From systematically monitoring the major (Na, Mg, Al, K, Ca, and Fe) and trace (Rb and Sr) elements, along with the Sr isotope composition, we have tried to estimate the contribution of long-range-transported Asian dust (“Kosa”) to the atmospheric aerosols.The results are summarized as follows:(1) The concentration of each element in the aerosols increased during the “Kosa” period. The increase was particularly obvious in samples collected on 8 April 2000, when the “Kosa Phenomenon” was observed at all the sampling sites in Japan, 2 days after a very heavy dust storm had occurred in China.(2) The Rb–Sr isotopic diagram shows a two-component mixing relationship: one with a high ⁸⁷Sr/⁸⁶Sr ratio and a high ⁸⁷Rb/⁸⁶Sr ratio, and the other with a low ⁸⁷Sr/⁸⁶Sr ratio and a low ⁸⁷Rb/⁸⁶Sr ratio. There is a significant difference between that of the expected end member of the Asian dust and that of the reported Asian loess, which is thought to be the possible source of the components of the “Kosa”, although the lower component is consistent with the local component at Wako.(3) Plots of the ⁸⁷Sr/⁸⁶Sr ratio vs the Ca/Al and Sr/Al ratios support a two-component mixing suggested by the Rb–Sr systematics, and they indicate that the contributing continental soil components to the “Kosa” aerosols should be composed of the silicate fraction of Asian loess.(4) The discrepancy in the Rb–Sr systematics between the expected end member and the possible sources may be caused by the dissolution of the Ca-bearing minerals via long-range dust transport, or by a combination of source characteristics and grain size separation.     

Development of the high spatial resolution EMICAT2000 emission model for air pollutants from the north-eastern Iberian Peninsula (Catalonia, Spain)

Ozone (O(3)) pollution episodes take place in Catalonia (NE of the Iberian Peninsula), mainly during summertime. The complex O(3) behaviour could be understood by using a Chemical Transport Model (CTM). Emission inventories provide the spatial and temporal emissions distribution of the O(3) precursors and other pollutants required by this approach. We developed the EMICAT2000 model with high spatial (cells of 1 km(2)) and temporal (1h) resolutions, to estimate the emissions during the year 2000 from Catalonia. Total annual emissions were 107 kt yr(-1) of NO(x), 137 kt yr(-1) of NMVOC, 267 kt yr(-1) of CO, 65 kt yr(-1) of SO(2), 24 kt yr(-1) of TSP and 32,175 kt yr(-1) of equivalent CO(2). Main NO(x) sources are on-road traffic (58%) and industries (38%). Main NMVOC sources are on-road traffic (36%), vegetation (34%) and use of solvents (13%). Speciation was established according to the Carbon Bond IV mechanism. EMICAT2000 generates directly the data files required for the third generation CTM Models-3/CMAQ.     

Chemical and strontium isotope characterization of rainwater in karst virgin forest,Southwest China

Strontium isotope ratios and concentrations of Ca²⁺, NH₄⁺, Na⁺, K⁺, Mg²⁺, Cl^?, SO₄^2?, NO₃^? and Al³⁺, Sr²⁺ were measured for 52 rainwater samples collected in virgin forest in a rural region between May 2007 and Dec. 2008. The rainwater pH values vary from 4.1 to 7.2 with a volume weight mean (VWM) value of 5.40. 40 of 52 samples have pH value above 5.0, indicating that the regional rainwater was not acidic. Among anions and cations, sulphate concentration (40.4 μeq l^?1, VWM) is the highest in the rainwater, followed by ammonium and calcium (30.2 and 20.8 μeq l^?1, VWM). Rainwater quality is characterized by low salinity and neutralized pH.The chemical compositions and ⁸⁷Sr/⁸⁶Sr ratios of the rainwater samples vary considerably. Using Na⁺ concentration as an indicator of marine origin, the proportions of sea salt and crustal elements were estimated from elemental ratios. The ⁸⁷Sr/⁸⁶Sr ratios were used to characterize different sources base on the data sets of this study and those from literatures. Such sources include weathering of limestone (⁸⁷Sr/⁸⁶Sr = 0.7075), remote soil dust (⁸⁷Sr/⁸⁶Sr > 0.7135) and anthropogenic source (fertilizers: ⁸⁷Sr/⁸⁶Sr = 0.7079). The results of the present study suggest that one likely source for high ammonium and calcium concentration is local soil. Due to a large contribution of these cations to the sulphate neutralization action, the rainwater in this region displays non-acidity, and thus has not significant environmental impact. The wet precipitation in the karst virgin forest in Guizhou province is strongly influenced by natural sources rather than anthropogenic sources.     

Fluxes of oxidised and reduced nitrogen above a mixed coniferous forest exposed to various nitrogen emission sources

Concentrations of nitrogen gases (NH(3), NO(2), NO, HONO and HNO(3)) and particles (pNH(4) and pNO(3)) were measured over a mixed coniferous forest impacted by high nitrogen loads. Nitrogen dioxide (NO(2)) represented the main nitrogen form, followed by nitric oxide (NO) and ammonia (NH(3)). A combination of gradient method (NH(3) and NO(x)) and resistance modelling techniques (HNO(3), HONO, pNH(4) and pNO(3)) was used to calculate dry deposition of nitrogen compounds. Net flux of NH(3) amounted to -64 ng N m(-2) s(-1) over the measuring period. Net fluxes of NO(x) were upward (8.5 ng N m(-2) s(-1)) with highest emission in the morning. Fluxes of other gases or aerosols substantially contributed to dry deposition. Total nitrogen deposition was estimated at -48 kg N ha(-1) yr(-1) and consisted for almost 80% of NH(x). Comparison of throughfall nitrogen with total deposition suggested substantial uptake of reduced N (+/-15 kg N ha(-1) yr(-1)) within the canopy.     

Hydrogen peroxide-assisted UV photodegradation of Lindane

Aqueous solutions of gamma-hexachlorocyclohexane (Lindane) were photolyzed (lambda=254 nm) under a variety of solution conditions. The initial concentrations of hydrogen peroxide (H(2)O(2)) and Lindane varied from 0 to 20 mM and 0.21 to 0.22 microM, respectively, the pH ranged from 3 to 11, and several concentration ratios of Suwannee River humic acid and fulvic acid were dissolved in the irradiated solutions. Lindane rapidly reacted, and the maximum reaction rate constant (9.7 x 10(-3) s(-1)) was observed at pH 7 and initial [H(2)O(2)]=1 mM. Thus, 90% of the Lindane is destroyed in approximately 4 min under these conditions. In addition, within 15 min, all chlorine atoms were converted to chloride ion, indicating that chlorinated organic by-products do not accumulate. The reactor was characterized by measuring the photon flux (7.04 x 10(-6) E s(-1)) and the cumulative production of *OH during irradiation. The cumulative *OH production during irradiation was fastest at an initial [H(2)O(2)]=5 mM (k=0.77 micro M s(-1)).     

Strontium isotope constraints on the seasonal variation of the provenance of base cations in rain water at Kawakami, Central Japan

The ⁸⁷Sr/⁸⁶Sr ratios in monthly precipitation in the forested basin at Kawakami, central Japan, varied seasonally from 0.709 to 0.711 in spring to as low as 0.7062 ± 0.0004 in autumn over nine years from 1987 to 1995. The seasonal variation can be explained in terms of the mixing of three sources of Sr: sea salt (⁸⁷Sr/⁸⁶Sr 0.70917), soluble eolian minerals originating from deserts in continental Asia ( 0.711), and biogenic materials growing on soils derived from the volcanic rock substrates in the vicinity ( 0.706). It is estimated that the contribution of sea-salt Sr into the Kawakami rain Sr is relatively constant (10 ± 5%) and that more than half of the Sr is of biogenic origin throughout the year except during spring rains when 50% of the Sr is due to the dissolution of Ca-minerals from Asian dusts. The dominant contribution of eolian components to spring rains is consistent with the high concentration of ³H, which is typical of air masses from Asia.     

Laboratory migration experiments with radionuclides and natural colloids in a granite fracture

Natural colloids in groundwater could facilitate radionuclide transport, provided the colloids are mobile, are present in sufficient concentrations and can adsorb radionuclides. This paper describes the results of a laboratory migration study carried out with combinations of radionuclides and natural colloids within a fracture in a large granite block to experimentally determine the impact of colloids on radionuclide transport. The 85Sr used in this study is an example of a moderately sorbing radionuclide, while the 241Am is typical of a strongly sorbed radionuclide with very low solubility. The natural colloids used in this study were isolated from granite groundwater from Atomic Energy of Canada (AECL) Underground Research Laboratory (URL), and consisted of mostly 1-10 nm organic colloids, along with lesser amounts of 10-450 nm colloids (organics and aluminosilicates). The measured coefficients for radionuclide sorption onto these colloids were between 3 x 10(2) and 1 x 10(3) ml/g for 85Sr, and between 7 x 10(4) and 7 x 10(5) mg/l for 241Am. The 85Sr sorption on the natural colloids appeared to be reversible. Migration experiments in the granite block were carried out by establishing a flow field between two boreholes (out of a total of nine) intersecting a main horizontal fracture. These experiments showed that dissolved 85Sr behaved as a moderately sorbing tracer, while dissolved 241Am was completely adsorbed by the fracture surfaces and showed no evidence of transport. However, when natural colloids were injected together with dissolved 241Am, a small amount of 241Am transport was observed, demonstrating the ability of natural colloids to facilitate the transport of radionuclides with low solubility. Natural colloids had only a minor effect on the transport of 85Sr. In a separate experiment to test the effect of higher colloid concentrations on 85Sr migration, synthetic colloids were produced from Avonlea bentonite. The introduction of a relatively high concentration of bentonite colloids actually reduced 85Sr transport because, compared to natural colloids, the bentonite colloids were less mobile and they sorbed 85Sr more strongly.     

Concentrations and possible sources of polychlorinated biphenyls in the surface water of the Yangtze River Delta, China

In this study, polychlorinated biphenyls (PCBs) pollution in the surface water of the Yangtze River Delta (YRD) was investigated. A total of 26 samples were collected from water bodies in three cities within the YRD during the dry season from October to November of 2009. The total PCBs (dissolved plus particulate) ranged from 1.23 to 16.6 ng L(-1) and were dominated by tri-, tetra-, and penta-chlorinated biphenyls. The mean PCBs in the Beijing-Hangzhou Grand Canal and the Yangtze River were 8.84 and 3.36 ng L(-1), respectively. A t-test showed that there were no significant differences in the concentration of samples from the metropolitan area and the development zone. According to the Chinese national environmental quality standards for surface water (GB 3838-2002), the concentrations of PCBs observed in this study do not pose a hazard to aquatic or human health. Overall, this study described the PCB concentration and homolog distribution patterns in one of the most rapidly developing areas in China, and the results can be used as reference levels for future PCB monitoring programs.     

Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. Part II: hydrolysis reactions

The effect of dissolved humic acid (HA) on two types of hydrolysis reactions was investigated: (I) dehydrochlorination of gamma-hexachlorocyclohexane (HCH) and 1,1,2,2-tetrachloroethane (TeCA) as a reaction involving hydroxide ions (OH(-)) and (II) hydrolysis of 1-octyl acetate (OA) which is catalyzed by H(+) at the applied pH value (pH 4.5). The rate of TeCA hydrolysis was not affected by addition of 2 g l(-1) of HA at pH 10 (k' = 0.33 h(-1)) but HCH hydrolysis was significantly inhibited (k' = 4.6 x 10(-3) h(-1) without HA and 2.8 x 10(-3)h(-1) at 2 g l(-1) HA). HCH is sorbed by 51% whereas TeCA sorption is insignificant at this HA concentration. Sorbed HCH molecules are effectively protected due to electrostatic repulsion of OH(-) by the net negative charge of the HA molecules. In contrast, OA hydrolysis at pH 4.5 (k' = 1.6 x 10(-5) h(-1)) was drastically accelerated after addition of 2 g l(-1) HA (k' = 1.1 x 10(-3) h(-1)). The ratio of the pseudo-first-order rate constants of the sorbed and the freely dissolved ester fraction is about 70. H(+) accumulation in the microenvironment of the negatively charged HA molecules was suggested to contribute to the higher reaction rate for the sorbed fraction in case of this H(+)-catalyzed reaction. Analogous effects from anionic surfactants are known as micellar catalysis.     

Formation of leadhillite and calcium lead silicate hydrate (C-Pb-S-H) in the solidification/stabilization of lead contaminants

In this study, we have investigated the structure of Pb-doped solidified waste forms (SWF) for assessment of lead fixation. A large quantity of lead precipitates produced during the S/S, based upon the results of cement-water solution analysis, X-ray diffraction and electron probe microanalysis/electron dispersive spectroscopy investigations, have been shown to be principally leadhillite (lead carbonate sulfate hydroxide, Pb(4)SO(4)(CO(3))(2)(OH)(2)), lead carbonate hydroxide hydrate (3PbCO(3).2Pb(OH)(2).H(2)O) and two other unidentified lead salts. In the long curing, the lead species dissolved from the lead precipitates are fixed into the cement matrix, forming a gelling calcium lead silicate hydrate during cement-based solidification. On leaching the lead precipitates such as leadhillite were markedly dissolved/released and some dissolved lead species were adsorbed to silicate-rich surface of leached SWF with the subsequent formation of mainly amorphous gel of calcium lead silicate hydrate.     

Levels and spatial distribution of chlorophenols - 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol in surface water of China

The chlorophenol pollutants (CPs) have been reported to occur at relatively high concentrations in some Chinese waters. To map the distribution of CPs in the surface water throughout China, samples were collected from over 600 sites in the seven major watersheds and three drainage areas. The samples were analyzed for the representative CPs including 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol. In general, it was observed that 2,4-dichlorophenol and 2,4,6-trichlorophenol were more frequently detected at higher concentrations in the rivers of North China compared with those of South China. High concentration sites of 2,4-dichlorophenol and 2,4,6-trichlorophenol mainly occurred in the Yellow River, Huaihe River, and Haihe River watersheds, while pentachlorophenol contamination mainly occurred in the Yangtze River watershed. The pentachlorophenol was the most ubiquitous CPs being detected in 85.4% of samples (median=50.0ngl(-1); range <1.1-594.0ngl(-1)), 2,4-dichlorophenol was detected in 51.3% (median=5.0ngl(-1); range <1.1-19960.0ngl(-1)) and the 2,4,6-trichlorophenol was detected in 54.4% of water samples (median=2.0ngl(-1), range <1.4-28650.0ngl(-1)). The results of this investigation indicated that 2,4-dichlorophenol and 2,4,6-trichlorophenol contaminations of Yellow River, Huaihe River, and Haihe River watersheds were of particular concern, while the pentachlorophenol contamination mainly occurred in the Yangtze River watershed. These results showed that CPs contamination in the surface water of China was similar to other places of the world.     

Distribution patterns of PAHs and trace elements in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from different forest communities: a case study, south-central Poland

Twenty samples of the moss species Hylocomium splendens and Pleurozium schreberi were collected at 10 sites of the Holy Cross Mountains (south-central Poland) and analyzed for 16 polycyclic aromatic hydrocarbons and 33 elements. The ring sequence of PAHs in the moss samples is: 4 (92-1040 ng x g(-1))>3 and 5 (21-272 ng x g(-1))>6 (<5-131 ng x g(-1)). H. splendens accumulates PAHs more effectively than P. schreberi, and therefore the former may be regarded as a better bioindicator of PAHs. No correlation was found between concentrations of PAHs and elements. However, both H. splendens and P. schreberi shows different bioaccumulative capabilities depending on the plant communities. The mosses growing in the dry pine forest Cladonio-Pinetum reveal higher levels of Fe, Na, Sr, Ti, Cr, Mo, Ni, V and higher mean concentrations of summation operator16 PAHs, whereas those from the continental coniferous forest Querco roboris-Pinetum are highlighted by elevated levels of B, Ca, K, Mg, Mn, P, Rb and Sb and lower mean concentrations of summation operator16 PAHs. These differences seem to be brought about by a higher biodiversity of the second forest type and its higher productivity that favors more effective cycling of elements.     

Vertical fluxes and accumulation of PCBs in coastal sediments of the Río de la Plata estuary, Argentina

Settling particles and underlying sediments collected at 1, 2.5 and 4 km along offshore transects in the urbanized sector of the Río de la Plata were analyzed to evaluate the sources and accumulation of PCBs. Total PCB concentrations range from <0.1 to 100 ng g(-1) and include variability associated to North-South and offshore gradients reflecting the impact of coastal discharges. Highest concentrations were recorded in the industrialized Central area close to Buenos Aires (61+/-37 ng g(-1) at 1 km) relative to cleaner northern stations (3.6+/-2.2 ng g(-1)) and southward sites (37+/-2.8 ng g(-1)), affected by transport of particulate PCBs by coastal currents. Sediment traps deployed in the Central area revealed large depositional fluxes of total matter (361+/-124 gm(-2)day(-1)) and PCBs (26+/-19 microg m(-2)day(-1)) and high sedimentation rates (5.0+/-1.7 cm yr(-1)). Uniform PCB concentrations (66-89 ng g(-1)) down to 20 cm in sediment cores suggest continued PCB discharges during the last 4 years. PCB composition was dominated by hexa (43+/-6.4%), hepta (23+/-5.1%) and pentachlorobiphenyls (21+/-5.5%) with lower proportions tri-tetra (7.4+/-5.4%) and higher chlorinated congeners (5.1+/-3.3%). A consistent weathering pattern with loss of 3-5 chlorobiphenyls and enrichment in higher chlorinated PCBs corresponding to a shift from a 1:1 to a 1:3 1254:1260 Aroclor mixture, was observed offshore. A principal component analysis performed with the relative contribution of PCB congener classes confirmed the offshore weathering pattern indicating that transformer oils containing Aroclor 1254-1260 are the most probable sources. Sediment inventories, sediment trap fluxes and Fugacity II calculations indicate an accumulation approximately 500-800 kg PCB in superficial sediments of this coastal environment.     

Application of molluscs for radioecological monitoring of the Chernobyl outburst

Accumulation of radionuclides was studied in molluscs from the territories polluted by the Chernobyl outburst. In addition to radiochemical evaluation of (90)Sr, a simple method of beta-radiometry of shells was applied which allowed processing of extensive samples and mapping of contamination of large territories: the Dnieper drainage area and the Kiev administrative region. Pre-Hiroshima and pre-Chernobyl radioactivity was investigated in museum collections. Differences in (90)Sr accumulation in molluscs of different genera were demonstrated for freshwater and terrestrial snails, an especially high accumulation factor was found in Helix. Indices of relative accumulation were calculated treating Lymnaea stagnalis as a standard. All the measurements were recalculated to this standard in order to provide comparisons between sampling sites disregarding collected species and to reduce variance before mapping. Based on shell beta-activity measurements, the average accumulation factor for (90)Sr in Lymnaea compared to its concentration in the river water was about 5000, its transfer factor compared to the soil contamination was about 0.1 m(2) kg(-1), figures for (137)Cs were smaller by an order of magnitude. Inverse dependence between free calcium content in the environment and the transfer factor was demonstrated, as well as a difference in (90)Sr/(137)Cs ratio in molluscs collected on different tracks of Chernobyl pollution. Monitoring the biologically accessible and biologically active fraction of (90)Sr contamination, the shell beta-activity above 15 kBq kg(-1) indicates a dangerous level of contamination for the human population.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.     

Artificial acidification of a non-acidic and an acidic headwater stream in Maine, USA

Two headwater streams with low DOC and different pHs (4.5-4.8 and 5-6.5) were acidified with H2SO4 to pH 4.1 and 4.5, respectively, for 24-h periods. Neutralization of the added acid occurred by protonation of ANC (HCO3-dominated in the higher pH stream), desorption of Ca (< 15 microeq litre(-1)) and Mg (<6 microeq litre(-1)), and desorption and dissolution of AL (<250 microg litre(-1)) from the stream bed. The concentrations of dissolved organic carbon (DOC) remained constant within the experimental reaches. The concentrations of Na, K an H4SiO4 also remained constant, indicating no detectable increase in the rate of chemical weathering in the stream bed. After acid addition was stopped, concentrations of Ca, Mg and Al decreased to below background, indicating reversible ion exchange as the principal mechanism for the mobility of Ca and Mg and to a lesser extent for Al. Repeated acidifications indicated that significant regeneration of cations on the exchange surfaces of the stream substrate occurs rapidly.     

The effective source area of 90Sr for a stream near Chernobyl, Ukraine

Remediation of streams impacted by non-point source contaminants requires an understanding of both the areas within a watershed that are contributing contamination to streams and the pathways of contaminant migration to streams. From 1998 to 2002, we studied the migration of 90Sr in the Borschi watershed, a small (8.5 km2) catchment three km south of the Chernobyl Nuclear Power Plant, Ukraine. Fuel particles, distributed in a heterogeneous pattern across the watershed, are weathering and releasing 90Sr from the fuel matrix. Depletion of (90)Sr, evaluated in comparison to the immobile fission product europium-154, is occurring in the channel and wetland sediment. Channel sediments are uniformly depleted in 90Sr with depth. In wetland sediments, there is a zone of depletion in the top 10 cm and a zone of accumulation at depths from 10 to 25 cm. Estimates of 90Sr depletion are used to map the effective source area that has contributed (90)Sr loading to the main channel. The effective source area includes channel bottom sediments, a wetland in the central region of the watershed, and periodically flooded soils surrounding the wetland. The total depletion from the effective source area is estimated to be 36 +/- 7 x 10(10) Bq. Based on observations of stream flow rate and water quality in 1999-2001, the annual 90Sr removal rate from the watershed is estimated to be 1.4 +/-0.2 x 10(10) or 1.5% of the inventory per year. When extrapolated over a 15-year period following the Chernobyl accident, the last value is in reasonable agreement with the estimated depletion of the source area based on 90Sr/154Eu ratios. The 90Sr yearly leaching rate considering the whole watershed is 0.2% while the 90Sr leaching rate considering the effective source area is an order of magnitude higher. Most of the 90Sr release in the watershed has originated from an effective source area of 0.62 km2, or 7% of the watershed area.