Mobilization of aluminium and deposition on fish gills during sea salt episodes--catchment liming as countermeasure

Episodic events may be critical with respect to aluminium (Al) toxicity in moderately acidified salmon rivers. The present work demonstrates that sea salt episodes enhance the toxicity of Al in acidic rivers. The documented sea salt episode (300 [micro sign]M Cl) mobilized positively charged Al species (0.4 to 1.1 [micro sign]M Al(i)), enhanced the Al accumulation on fish gills (0.9 to 10 [micro sign]mol g(-1) dw) and caused increased stress responses (6 to15 mM blood glucose) in fish. Accumulated Al on gills remained high several days after the episode. The presented results are based on a six-week field study in two tributary rivers on the west coast of Norway. Changes in the river water qualities and Al speciation were followed using in situ fractionation techniques. Al accumulation on gills and stress responses were followed for Atlantic salmon (Salmo salar) kept in tanks continually exposed to the changing water quality. The potential mobilization of Al from the two catchments was studied by extracting soils with diluted seawater (salinity of 3). To counteract Al toxicity, one of the tributary catchments has been limed. The potential mobility of Al by sea salt was lower in limed soils compared to acid soils, and the Al deposition on fish gills (<3.5 [micro sign]mol g(-1) dw) and associated stress responses stayed low during the sea salt episode in the river draining the limed catchment. Thus, for acid river systems in coastal areas, catchment liming should be considered as a useful countermeasure for Al toxicity.     

Association of plutonium with sediments from the Ob and Yenisey Rivers and Estuaries

The present study applied sequential extraction techniques to investigate the binding and mobility of plutonium (Pu) in sediments from the rivers and estuaries of the Ob and Yenisey. As a study site, the Ob and Yenisey are particularly interesting as both rivers have weapons-grade Pu sources in their catchment areas, including the Russian Pu production and reprocessing plants at Mayak, Tomsk-7 and Krashnoyarsk, and the Semipalantinsk nuclear weapons testing site in Kazakhstan. Plutonium activity and ²⁴⁰Pu/²³⁹Pu ratios were determined using accelerator mass spectrometry (AMS). Sequential extractions showed that between 47 and 80% of the Pu in Yenisey River sediments and 35–53% of the Pu in soils around the Techa River are mobilized with weak oxidising agents, which can indicate that Pu is bound to organic material. In contrast, Pu in Ob and Yenisey Estuarine sediments was more strongly bound, with 60–100% being found in the HNO₃-extractable fraction. This change in speciation could reflect either that Pu bound to organic material in the Techa and Yenisey River sediments becomes more fixed to the sediments with time, or that organic-bound Pu is mobilized and released to the water when the sediments encounter the more saline water of the Ob and Yenisey estuaries. In general, ²⁴⁰Pu/²³⁹Pu ratios were relatively consistent between different extraction fractions, although, in whole sediments, an increase in ratio was observed with distance from the source. This reflects the increased influence of weapon fallout from catchment runoff within the river systems, as compared to the weapons-grade sources close to the production and reprocessing plants. Knowledge of Pu speciation in the Ob and Yenisey Rivers, and the processes controlling its behaviour in estuarine systems, can improve predictions of its transfer and subsequent environmental impact to Arctic Seas.     

Challenges in radioecology

Today, radioecology covers a broad scientific field; from the source to long term environmental impact from ionizing radiation. To summarize key challenges within radioecology, the present paper focuses upon knowledge gaps related to processes, mechanisms and variables contributing most to the overall uncertainties in environmental impact assessments. A series of sources related to the nuclear weapon cycle and the civil nuclear cycle has contributed, is still contributing or can potentially contribute to release of radionuclides to the environment in the future. The speciation of most radionuclides depends on the source and release conditions, and will influence ecosystem transport, biological uptake, doses and effects in flora and fauna. Radionuclides may also co-occur in contaminant mixtures (e.g., metals, organics), which potentially could lead to synergisms or antagonisms. Thus, challenges associated with the links between the source or release term – radionuclide speciation – ecosystem transfer – exposure – response relationships are highlighted.     

Analytical techniques in studies of aluminium-species in aqueous solutions

Health effects associated with biological uptake of Al depend on the dietary intake (dose) and on bioavailable Al-species originally present in the diet or mobilised from inert species in the gastro-intestinal tract.Analytical techniques capable of fractionating species according to size and charge properties are available for aqueous solutions especially natural waters. When the techniques are combined,i.e. fractionation according to size (e.g. molecular weights) prior to the fractionation according to charge properties, the analytical results are easier to interpret. Thus the quality of the input data for modelling purposes is improved. For biological materials, however, the results obtained using different techniques are operationally defined only.     

Recovery from acidification in European surface waters: a view to the future

There is now overwhelming documentation of large-scale chemical recovery from surface water acidification in Europe, but to date there has been little documentation of biological recovery. Modelling studies based on current emission reduction plans in Europe indicate that there will be further chemical recovery. The uncertainties in these scenarios mainly relate to the future behavior of nitrogen in the ecosystem and the effects of climate change. Four major climate-related confounding factors that may influence the chemical and biological recovery process are: i) increased frequency and severity of sea-salt episodes; ii) increased frequency and severity of drought; iii) increased turnover of organic carbon; iv) increased mineralization of nitrogen. International cooperative work to abate acidification has so far been very successful, but there is still a long way to go, and many potential setbacks. It is essential that future development of water chemistry and aquatic biota in acidified waterbodies continue to be monitored in relation to further emission reductions of S and N and future effects of climate change.     

Solid state speciation and potential bioavailability of depleted uranium particles from Kosovo and Kuwait

A combination of synchrotron radiation based X-ray microscopic techniques (μ-XRF, μ-XANES, μ-XRD) applied on single depleted uranium (DU) particles and semi-bulk leaching experiments has been employed to link the potential bioavailability of DU particles to site-specific particle characteristics. The oxidation states and crystallographic forms of U in DU particles have been determined for individual particles isolated from selected samples collected at different sites in Kosovo and Kuwait that were contaminated by DU ammunition during the 1999 Balkan conflict and the 1991 Gulf war. Furthermore, small soil or sand samples heavily contaminated with DU particles were subjected to simulated gastrointestinal fluid (0.16 M HCl) extractions. Characteristics of DU particles in Kosovo soils collected in 2000 and in Kuwait soils collected in 2002 varied significantly depending on the release scenario and to some extent on weathering conditions. Oxidized U (+6) was determined in large, fragile and bright yellow DU particles released during fire at a DU ammunition storage facility and crystalline phases such as schoepite (UO₃·2.25H₂O), dehydrated schoepite (UO₃·0.75H₂O) and metaschoepite (UO₃·2.0H₂O) were identified. As expected, these DU particles were rapidly dissolved in 0.16 M HCl (84 ± 3% extracted after 2 h) indicating a high degree of potential mobility and bioavailability. In contrast, the 2 h extraction of samples contaminated with DU particles originating either from corrosion of unspent DU penetrators or from impacted DU ammunition appeared to be much slower (20–30%) as uranium was less oxidized (+4 to +6). Crystalline phases such as UO₂, UC and metallic U or U–Ti alloy were determined in impacted DU particles from Kosovo and Kuwait, while the UO_2,34 phase, only determined in particles from Kosovo, could reflect a more corrosive environment. Although the results are based on a limited number of DU particles, they indicate that the structure and extractability of DU particles released from similar sources (metallic U penetrators) will depend on the release scenarios (fire, impact) and to some extent environmental conditions. However, most of the DU particles (73–96%) in all investigated samples were dissolved in 0.16 M HCl after one week indicating that a majority of the DU material is bioaccessible.     

Screening for Stockholm Convention persistent organic pollutants in the Bosna River (Bosnia and Herzogovina)

The Stockholm Convention, which aspires to manage persistent organic pollutants (POPs) at the international level, was recently ratified in Bosnia and Herzegovina (BiH). Despite this fact, there is in general a paucity of data regarding the levels of POPs in the environment in BiH. In the present study, screening for POPs was conducted in one of the country’s major rivers, the Bosna. A two-pronged approach was applied using passive samplers to detect the freely dissolved and bioavailable concentrations in the water phase and sediment analysis to provide an integrated measure of historical contamination. At several places along the river, the concentrations of polycyclic aromatic hydrocarbons (PAH) were high and exhibited potential for both chronic and acute effects to biota. River water also showed elevated concentrations of PAH, up to 480 ng L^?1 near the city of Doboj, and diagnostic ratios suggested combustion sources for the contamination present in both types of sample. The levels of the other contaminants measured—polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers—were generally low in the water phase. However, PCBs and some OCPs were present in river sediments at levels which breach the international criteria and thus suggest potential for ecological damage. Additionally, the levels of heptachlor breached these criteria in many of the sites investigated. This study presents the first screening data for some of these Stockholm Convention relevant compounds in BiH and reveals both low concentrations of some chemical groups, but significant point sources and historic contamination for others.     

Fish mortality during sea salt episodes--catchment liming as a countermeasure

Aluminium (Al) toxicity is usually associated with acid rain and acidified freshwater systems. The present work demonstrates that acute fish mortality (50%) also occurs in moderate acidified salmon rivers during sea salt episodes. Furthermore, catchment liming was proved to be an efficient measure to counteract the fish toxicity. The impact of sea salt episodes on river water qualities and on Atlantic Salmon (Salmo salar L.) was studied in two rivers situated at the west coast of Norway. During February-May 2002, fish were kept in tanks and continually exposed to the changing water qualities. Changes in Al-species were followed using in situ fractionation techniques. During storm events and high sea salt deposition, the sea salt concentration increased (190 to 580 microM Cl), pH decreased (pH 5.3 to 4.6) and the concentration of low molecular mass (LMM) cationic Al-species (Al(i)) increased (0.7 to 3.0 microM) in the river. Subsequently, Al accumulated in fish gills (6 to 19 micromol g(-1) dw) causing ionoregulatory and respiratory failures as well as mortality. In water the concentration of LMM Al(i) stayed enhanced during four weeks, while the physiological stress responses in surviving fish remained high for a longer time (>eight weeks). To counteract Al toxicity, one of the tributary catchments had been limed four years earlier. Due to catchment liming (1000 kg ha(-1)) the water concentration of LMM Al(i)(<0.7 microM) and the Al accumulation in gills remained relatively low (<7 micromol g(-1) dw) during the storm and no fish mortality occurred.     

Oxidation states of uranium in depleted uranium particles from Kuwait

The oxidation states of uranium in depleted uranium (DU) particles were determined by synchrotron radiation based mu-XANES, applied to individual particles isolated from selected samples collected at different sites in Kuwait. Based on scanning electron microscopy with X-ray microanalysis prior to mu-XANES, DU particles ranging from submicrons to several hundred micrometers were observed. The median particle size depended on sources and sampling sites; small-sized particles (median 13 microm) were identified in swipes taken from the inside of DU penetrators holes in tanks and in sandy soil collected below DU penetrators, while larger particles (median 44 microm) were associated with fire in a DU ammunition storage facility. Furthermore, the (236)U/(235)U ratios obtained from accelerator mass spectrometry demonstrated that uranium in the DU particles originated from reprocessed fuel (about 10(-2) in DU from the ammunition facility, about 10(-3) for DU in swipes). Compared to well-defined standards, all investigated DU particles were oxidized. Uranium particles collected from swipes were characterized as UO(2), U(3)O(8) or a mixture of these oxidized forms, similar to that observed in DU affected areas in Kosovo. Uranium particles formed during fire in the DU ammunition facility were, however, present as oxidation state +5 and +6, with XANES spectra similar to solid uranyl standards. Environmental or health impact assessments for areas affected by DU munitions should therefore take into account the presence of respiratory UO(2), U(3)O(8) and even UO(3) particles, their corresponding weathering rates and the subsequent mobilisation of U from oxidized DU particles.     

Remobilisation of 109Cd, 65Zn and 54Mn from freshwater-labelled river sediments when mixed with seawater

A major fraction of trace metals transported by rivers is associated with sediments, especially during flooding, when erosion and resuspension increase sediment loads. Upon contact with seawater in estuaries, changes in ionic strength and pH may remobilise trace metals from sediment surfaces into more bioavailable forms. The objective of the present work was to investigate time-dependent interactions between trace metals and freshwater sediments and their potential remobilisation upon contact with seawater. Two river sediments (one organic and one inorganic) were labelled with 109Cd2+, 65Zn2+ and 54Mn2+ radioactive tracers for periods up to 6 months. Sorption of tracers occurred rapidly (> or = 80% sorption, < 1 h), followed by a slower approach to pseudoequilibrium. Kd(6 months) were estimated as 460, 480 and 2200 ml/g (inorganic sediment) compared to 5300, 4000 and 1200 ml/g (organic sediment) for 109Cd, 65Zn and 54Mn, respectively. Remobilisation of tracers from labelled sediments was studied using sequential extractions. Artificial seawater extracts simulated an estuarine environment. Subsequent extractions provided information about more strongly sorbed tracer fractions within sediments. Remobilisation of 109Cd by seawater was significant (> 65%) and least affected by sediment type or freshwater labelling time. Redistribution of Cd to strongly bound phases was minimal (4% and 1% of 109Cd in strongly oxidisable fractions). Seawater remobilisation of 65Zn was significantly greater from the organic sediment (54%) compared to the inorganic sediment (8%), where a large fraction of 65Zn (14%) became irreversibly bound. Similarly, more 54Mn was remobilised by seawater from the organic sediment than the inorganic sediment (66% and 3% remobilised, respectively), i.e., 54Mn became more strongly bound in the inorganic sediment. A simple three-box model, based on first-order differential equations, was used to describe the interaction between tracers in spiked freshwater and two operationally defined sediment fractions ("seawater exchangeable" and "seawater unexchangeable") up to 6 months of freshwater labelling. Model simulations were fitted to experiment data and apparent rate constants were calculated using numerical optimisation methods. Sorption ratios from modelling data (i.e., k1/k2) were greater for organic compared to inorganic sediments, while fixation ratios were higher in inorganic sediments. In conclusion, trace metals can be remobilised from sediments on contact with seawater in estuaries. High organic content in sediments increased initial sorption of tracers but inhibited redistribution to more strongly bound fractions over time, resulting in greater remobilisation of tracers when in contact with seawater.