Dynamics of aluminum speciation in forest-well drainage waters from the Rhode River watershed, Maryland

This paper reports an investigation of the dynamics of aluminum (Al) speciation in the forest-well waters from study site 110 of the Rhode River watershed, a representative sub-unit of Chesapeake Bay. Seasonal changes of Al speciation are evaluated by a modified MINEQL computer model using chemical equilibrium calculation. It was found that Al-F and Al-Org complexes were the dominate forms, whereas toxic forms of Al3+ and Al-OH were not significant. This indicates that Al toxicity is not very serious in the Rhode River area due to the high concentrations of fluoride and organic materials, even though sometimes pH is very low (approximately 4). Increased H+ or some other associated factors may be responsible for the decline in fish and amphibian population on the watershed.     

Uranium series isotopes in the Avon Valley, Nova Scotia

An U-series isotopic study was carried out in the waters of the Avon Valley, Nova Scotia. The fresh and acidic recharge waters flow rapidly through the watershed composed of a granitic highland and a sedimentary, largely carbonate, lowland plain, before draining to the sea. There is no significant anthropogenic pollution; but, naturally elevated U levels can be encountered within the bedrock. Nonetheless, the U concentrations of the surface and groundwater are low (generally within the range of several hundredths to several tenths of a microg l(-1)), except in the proximity to weathering of U mineralization. The dissolved U in the surface waters appears to be stabilized by organic rather than inorganic complexes. Both the groundwaters and surface waters have similar (234)U/(238)U activity ratios that rarely deviate from secular equilibrium by more than 20% throughout the watershed. The magnitude of the (234)U/(238)U activity ratio is not determined by lithology but rather by the weathering mechanism, the high rate of flushing, and the leaching of local U mineralization. Dissolved Ra is consistently absent. The dissolved Rn concentrations, though variable, are measurable even in surface waters. This may be due to a continual degassing from the U-enriched bedrock or release from local sites of U mineralization underlying the surface water sources.     

Tritium in surface waters of the Yenisei River basin

This paper reports an investigation of the tritium content in the surface waters of the Yenisei River basin near the Mining and Chemical Combine (MCC). In 2001 the maximum tritium concentration in the Yenisei River did not exceed 4 +/- 1 Bq l(-1), which is consistent with the data of 1998-99. However, it has been found that there are surface waters containing enhanced tritium as compared with the background values for the Yenisei River. For instance, in the Ploskii Stream and the Shumikha River the maximum tritium concentrations amount to 168 and 81 Bq l(-1), respectively. The source of tritium in these surface waters is the last operating reactor at the MCC, which still uses the Yenisei water as coolant. In water and sediment samples of the Bolshaya Tel River (a tributary of the Yenisei River) the tritium content turned out to be at least 10 times higher than the background values for the Yenisei River. The measurements conducted at the RPA RADON (Moscow) revealed not only tritium but also the artificial radionuclide (14)C in the Bolshaya Tel samples. The data obtained suggest that the Bolshaya Tel River receives the major part of tritium from sediments rather than from the water catchment area. This allows the conclusion that there is water exchange between the surface waters and the radioactively contaminated underground horizons of the "Severny" testing site.     

228Ra/226Ra/224Ra and 87Sr/86Sr isotope relationships for determining interactions between ground and river water in the upper Rhine valley

Ground and river waters of the upper Rhine valley (Alsace, France) were investigated for chemical composition of the major elements, Sr isotopes and radionuclides from the U and Th series. In particular, the isotope ratios and concentrations of Ra and Sr were used as geochemical tracers to distinguish between different types of water and their interactions. The bulk chemical analyses suggest that the surface waters in the Rhine valley can be described as mixtures between Ca-Na-HCO3-rich ground water and less mineralized slightly acidic river waters which have migrated through crystalline (mainly granitic) basement rocks of the Vosges mountains. Mixing of these waters yields positive correlation between bulk Sr, U, Ca and HCO3, indicating that carbonate-rich sediments are the main source of U and (non-radiogenic) Sr in the Rhine valley aquifers. The combination of the Ra and Sr isotope systems (228Ra/226Ra, 87Sr/86Sr) shows, however, that probably three sources contribute to the surface river waters in the upper Rhine valley, i.e. (i) a highly radiogenic crystalline component, (ii) a ground water source and, (iii) a third component from infiltrating Rhine water along the flow path of the parallel running river Ill in the northerly direction. The Sr and Ra isotope systems were also used to calculate small-scale mixing fractions of tributaries along the flow path of the Ill. Mixing ratios of non-pure end-member waters were determined using three isotope diagrams (i.e. 224Ra/226Ra vs. 228Ra/226Ra) and the results obtained with the Ra isotope system were found to be consistent with the data using Sr isotope relationships (i.e. 87Sr/86Sr vs. 1/Sr).     

Environmental fate of Ra in cation-exchange regeneration brine waste disposed to septic tanks, New Jersey Coastal Plain, USA: migration to the water table

Fate of radium (Ra) in liquid regeneration brine wastes from water softeners disposed to septic tanks in the New Jersey Coastal Plain was studied. Before treatment, combined Ra (²²⁶Ra plus ²²⁸Ra) concentrations (maximum, 1.54 Bq L⁻¹) exceeded the 0.185 Bq L⁻¹ Maximum Contaminant Level in 4 of 10 studied domestic-well waters (median pH, 4.90). At the water table downgradient from leachfields, combined Ra concentrations were low (commonly ≤0.019 Bq L⁻¹) when pH was >5.3, indicating sequestration; when pH was ≤5.3 (acidic), concentrations were elevated (maximum, 0.985 Bq L⁻¹ - greater than concentrations in corresponding discharged septic-tank effluents (maximum, 0.243 Bq L⁻¹)), indicating Ra mobilization from leachfield sediments. Confidence in quantification of Ra mass balance was reduced by study design limitations, including synoptic sampling of effluents and ground waters, and large uncertainties associated with analytical methods. The trend of Ra mobilization in acidic environments does match observations from regional water-quality assessments.     

Cosmogenic 22Na as an index of the residence time of water in freshwater basins: a review

The goal of this review is to draw attention to an opportunity for the use of cosmogenic (22)Na for dating young surface and underground waters. After 1961 when a significant quantity of (22)Na was released into the environment as a result of nuclear weapon tests, its concentrations in river waters were greatly increased, and a return to natural (cosmogenic) levels took until the mid-1980s. The studies made during this non-steady-state period showed that the one-box model for freshwater basin correctly describes the experimental data. For the 19 studied basins of Russia, the Baltic States and Japan, a calculation based on this model gave values for the mean residence time of water in the range from 4 to 23 years. Now, only cosmogenic (22)Na is in the environment, and it is the single cosmogenic radionuclide at present, which can serve as a steady-state tracer for dating young waters (up to some decades).     

The removal of uranium from mining waste water using algal/microbial biomass

We describe a three step process for the removal of uranium (U) from dilute waste waters. Step one involves the sequestration of U on, in, and around aquatic plants such as algae. Cell wall ligands efficiently remove U(VI) from waste water. Growing algae continuously renew the cellular surface area. Step 2 is the removal of U-algal particulates from the water column to the sediments. Step 3 involves reducing U(VI) to U(IV) and transforming the ions into stable precipitates in the sediments. The algal cells provide organic carbon and other nutrients to heterotrophic microbial consortia to maintain the low E(H), within which the U is transformed. Among the microorganisms, algae are of predominant interest for the ecological engineer because of their ability to sequester U and because some algae can live under many extreme environments, often in abundance. Algae grow in a wide spectrum of water qualities, from alkaline environments (Chara, Nitella) to acidic mine drainage waste waters (Mougeotia, Ulothrix). If they could be induced to grow in waste waters, they would provide a simple, long-term means to remove U and other radionuclides from U mining effluents. This paper reviews the literature on algal and microbial adsorption, reduction, and transformation of U in waste streams, wetlands, lakes and oceans.     

Unraveling the causes of the toxicity of extremely acid waters of volcanic origin

A river ecosystem in East Java, Indonesia, fed by a volcanic lake with high concentrations of dissolved metals and a low pH, was found to support only few macroinvertebrates. To unravel the causes of toxicity and to determine the level of dilution necessary to obtain non-toxic water, a bioassay was conducted with the fairy shrimp Thamnocephalus platyurus. A partial toxicity identification evaluation (TIE) approach was used with EDTA as a chelating agent to relate toxicity to pH and metal concentrations. Three water samples were tested, with pHs ranging from 0.72 to 4.5, and diluted with water from a neutral river to different degrees. The dilution factor necessary to achieve no more than 50% mortality in the Thamnotox test (Ldf(50)) varied from >300 at the most acidic site, to 7 for water of pH 2.6 and 1.5 for water of pH 4.5. Toxicity was best explained from both low pH and high concentrations of metals, especially Al and Fe. The key role of Al and Fe in the toxicity was confirmed by relating concentrations of the different compounds in the river water to toxicity data from the literature. EDTA addition did not significantly influence Ldf(50) or the lethal pH 50% (LpH(50)), suggesting a large effect, besides cationic components and pH, of anions (F, SO(4) and Cl).     

Acidification of lead/zinc mine tailings and its effect on heavy metal mobility

The acid-forming potential of lead/zinc (Pb/Zn) mine tailings at Lechang City of Guangdong Province was studied using both net acid generation (NAG) and acid-base accounting (ABA) methods. The pyritic and total sulfur contents of the tailings were 12.6% and 18.7%, respectively. The mean acid neutralization capacity (ANC) was 63.5 kg H2SO4/t while three oxidized tailings samples had an ANC less than zero. The NAG and net acid production potential (NAPP) values were 220 and 326 kg H2SO4/t, and both the NAG and NAPP results indicated that the tailings had a high acid-forming potential. NAG was more accurate than NAPP in predicting acid-forming potential of the tailings due to uncompleted oxidization of pyritic sulfur. Analysis of samples from two profile tests indicated that acidification mainly occurred at the surface (0-20 cm) and had little effects at deep layer of the tailings. Total concentrations of Pb, Zn, Cu, and Cd were increased greatly with depth at the acidified tailings profile, while heavy metal concentrations at different depths of nonacidified tailings profile were similar. The results indicated that depletion of heavy metals at the acidified surface was due to acidification. The diethylenetetramine pentaacetic acid (DTPA)-extractable Pb, Zn, Cu, and Cd concentrations of acidified tailings surface (0-20 cm) were significantly higher than those of nonacidified tailings, which further revealed that acidification enhanced the mobility of heavy metals in the tailings.     

Uranium-thorium disequilibrium in north-east Atlantic waters

In this paper we report and compare the concentrations of 234Th and 238U measured in surface and subsurface waters collected in the course of a sampling campaign in the north east Atlantic in June-July 1998. Dissolved 234Th concentrations in surface waters ranged from 5 to 20 Bq m(-3), showing a large deficiency relative to 238U concentrations (typically 42 Bq m-3). This disequilibrium is indicative of active 234Th scavenging from surface waters. Observed 234Th/238U activity ratios, together with corresponding 234Th particulate concentrations, were used to calculate mean residence times for 234Th with respect to scavenging onto particles (tau(diss)) and subsequent removal from surface waters (tau(part)). Residence times in the range 5-30 days were determined for tau(diss) and 4-18 days for tau(part) (n=14). In addition, ultrafiltration experiments at six stations in the course of the same expedition revealed that in north-east Atlantic surface waters a significant fraction (46+/-17%; n=6) of the thorium in the (operationally-defined) dissolved phase (<0.45 microm) is in colloidal form. These observations are consistent with the 'colloidal pumping' model in which it is assumed that 234Th is rapidly absorbed by colloidal particles, which then aggregate, albeit at a slower rate, into larger filterable particles. In essence, colloids act as intermediaries in the transition from the fully dissolved to the filter-retained (>0.45 microm) phase. Thus, the time (tau(c)) for fully dissolved 234Th to appear in the filter-retained fraction is dependent on the rate of colloidal aggregation. Here, we determined tau(c) values in the range 3-17 days.     

Evaluation of the pollution of the surface waters of Greece from the priority compounds of list II, 76/464/EEC directive, and other toxic compounds

The pollution of the surface waters of Greece from the priority compounds of 76/464/EEC Directive was evaluated. The occurrence of 92 toxic compounds, 64 of which belong to priority compounds of List II, candidates for List I, of 76/464/EEC Directive, was studied in surface waters and wastewater through the developed network of 62 sampling stations, which covers the whole Greek territory. The analytical determination was performed by Purge and Trap-Gas chromatography-Mass spectrometry for volatile and semivolatile organic compounds (VOCs), Gas Chromatography-Electron Capture Detection for organochlorine insecticides, Gas Chromatography-Nitrogen Phosphorous Detection for organophosphorous insecticides, High Performance Liquid Chromatography-Photodiode Array Detection for herbicides, and Electrothermal Atomic Absorption Spectrophotometry and Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) for metals and the toluene extractable organotin compounds. The concentrations of VOCs and insecticides detected in the surface waters of Greece were very low, whereas the concentrations of herbicides and metals ranged generally at moderate levels. VOCs were detected almost exclusively in the rivers and very rarely in the lakes, while the frequency of occurrence of insecticides, herbicides and metals was similar for rivers and lakes. Water quality objectives (WQO) and emission limit values (ELV) have been laid down in national legal framework for a number of compounds detected in the samples, in order to safeguard the quality of surface waters from any future deterioration.     

Discharge of pharmaceutical products (PPs) through a conventional biological sewage treatment plant: MECs vs PECs?

Pharmaceuticals for human use are consumed in significant quantities and their occurrence in aquatic systems has been reported by a number of authors. In the context of environmental risk assessment, there is an increasing interest in evaluating the discharge of pharmaceutical products to surface waters through sewage treatment plants (STP). This case study was carried out on a conventional biological treatment plant (Alès, France) and focused on a set of eleven drugs representing the main therapeutic classes. Measured environmental concentrations (MECs) range from the low ng L^? 1 to 1.5 µg L^? 1 in effluent and up to few hundred ng L^? 1 in receiving surface waters. There is a good agreement between MEC and predicted environmental concentration (PEC) values for seven of the eleven investigated drugs in STP effluent. There is not such a good match between PEC and MEC values in surface waters, and this highlights the limits of this approach, at the local scale.     

BOD-DO modeling and water quality analysis of a waste water outfall off Kochi, west coast of India

Water quality scenarios around an offshore outfall off Kochi were simulated using MIKE21 water quality model, assuming a high Biochemical Oxygen Demand (BOD=50 mg l(-1)) effluent discharge. The discharge is introduced into the model through an outfall located at a distance of 6.8 km from the shore at a depth of 10 m. Three scenarios were simulated with different discharge rates such as 2, 5 and 10 m3 s(-1), with BOD load of 8640, 21,600 and 43,200 kg day(-1) respectively. Model simulations were carried out to estimate the assimilation capacity of the waters off Kochi for the three discharge rates. The results show that for 10 m3 s(-1) effluent discharge, the initial BOD of 50 mg l(-1) reduced to 3.33 mg l(-1) at the outfall after 48 h. High BOD values were confined to an elliptical area of approximately 8 km2 around the outfall. Based on this, the assimilative capacity of the waters off Kochi in terms of BOD can be estimated as 38,000 kg day(-1). It is suggested that offshore waters could be used as a feasible alternative to the Kochi backwaters for the disposal of treated effluent.     

Studies of Np and Pu in the marine environment of Swedish-Danish waters and the North Atlantic Ocean

The long-lived anthropogenic radionuclides (237)Np, (239)Pu and (240)Pu were determined in marine environmental samples (seaweed and seawater) collected from Swedish-Danish waters and the North Atlantic Ocean at various locations on different occasions during the period 1991-2001. The measurements were performed with sector field Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and conventional alpha spectrometry. The (237)Np activity concentrations in Fucus vesiculosus and surface seawater from the Swedish west coast and Danish waters ranged from 0.16+/-0.02 to 1.02+/-0.09 mBq kg(-1) (dry weight) and 0.65+/-0.02 to 1.69+/-0.02 mBq m(-3), respectively, depending on the location and sampling year. Most of the (237)Np in these waters is believed to originate from the Sellafield nuclear reprocessing plant, with some contribution from global fallout. The (240)Pu/(239)Pu atomic ratios in F. vesiculosus samples are reported in this study with an overall average of 0.17+/-0.03. The (237)Np and (239)Pu activity concentrations observed in surface seawater collected in North Atlantic waters ranged from 0.16+/-0.01 to 0.62+/-0.08 mBq m(-3) and from 0.64+/-0.05 to 4.27+/-0.08 mBq m(-3), respectively, and the (237)Np/(239)Pu atomic ratios were a good indicator of conservative behaviour of Np in marine waters.     

Fertility status and management implications of wetland soils for sustainable crop production in Akwa Ibom State, Nigeria

Fertility status of soils of three wetland types in Akwa Ibom State, Nigeria, was investigated. The wetland types are Inland Valley (IV), Flood Plain (FP) and Mangrove (MG). The soils have silt-clay ratios above 0.15 and 0.25 indicating that they are of young parent materials with low degree of weathering and possible weatherable minerals for plant nutrition. The pH of the soils was near neutral (>6.4) when wet but extremely acid (>3.5) when dried indicating that the soils are potential acid sulphate soils. Organic matter content was high with mean values of 12.59, 6.03 and 3.20% for IV, FP and MG soils, respectively. Total N (nitrogen) was low except in IV soils where the value was above the 0.30% critical level. The C:N ratios were narrow with mean of 20.90, 12.17 and 12.12 for IV, FP and MG soils, respectively. The contents of basic cations [Calcium (Ca), Magnesium (Mg), Potasium (K) and Sodium (Na)] were low while acidic cations [Aluminium (Al) and Hydrogen (H)] were high. The Ca:Mg ratios were below the optimum range of 3:1 to 4:1 required for most crops. The Mg:K ratios were above 1.2, below which yields of crops like corn and soybean may be reduced. Effective cation exchange capacity (ECEC) was below the 20 cmol/kg. Percent base saturation was low (<38) indicating that the soils are potentially less fertile. Exchangeable Al and percent Al saturation were high, above 60% in IV and FP soils. Electrical conductivity was above the critical value of 2 dsm⁻¹ while exchangeable sodium percentage was less than 15. Available Phosphorus (P) and low, <10 ppm and free Fe₂O₃/clay ratios were <0.15. Positive correlation existed between silt and ECEC, implying that silt contributed to nutrient status of the soils. Generally, fertility status of the soil is low and would require maintenance of adequate organic matter, application of lime and organic and inorganic fertilizers, drainage and irrigation if the land is to be used for intensive/sustainable crop production. Readers should send their comments on this paper to: BhaskarNath@aol.com within 3 months of publication of this issue.     

Radon concentrations in groundwaters of the Polish part of the Sudety Mountains (SW Poland)

In the course of researches into radon occurrence in the groundwaters of the Polish part of the Sudety Mountains, conducted in various research centres in Poland, almost 1000 radon concentration determinations have been collected. These results have given the basis for an attempt to characterise the groundwaters of this region with respect to radon content. Radon concentrations oscillated within the range of 0.2-1645 Bq/dm3, with the arithmetic mean at 240.0 Bq/dm3 and the geometric mean at 106.7 Bq/dm3. The largest number of radon concentrations found in the Sudetic groundwaters ranged between ca. 3-6 and 1000 Bq/dm3. The values over 1000 Bq/dm3 can be considered anomalously high. They constitute 3.9% of all the results and occur around six localities within different geological units of the Sudety Mountains. These are shallow circulation, low mineralised groundwaters, which outflow from gneisses and granites. In the face of the fact that from 12.8% to 72.7% (depending on the adopted norm of maximum radon concentration for drinking waters) of the examined waters cannot be drunk directly without removing at least part of the radon, and in the face of the possibility of recognizing as many as 63.5% of the waters as potentially medicinal, extensive research of radon geochemistry in the Sudety Mountains area should be urgently undertaken.     

137Cs and 90Sr behavioural regularities in the southeastern part of the Baltic Sea

Variations in 137Cs concentrations were investigated over the period 1986-1997 in the southeastern part of the Baltic Sea, following the Chernobyl power plant accident. The rate of "self-cleaning" was demonstrated to be very slow, the average concentration of 137Cs in 1996 being almost the same as that measured directly after the accident, in 1986. Measurements of both 137Cs and 90Sr concentrations generally revealed homogeneous distributions in this region of the Baltic Sea, though patchy distributions did develop under some hydrometeorological conditions. Specifically, the 137Cs concentration distribution became heterogeneous with values varying in the range 60-92 Bq/m3 under south-southwesterly wind conditions whilst the 90Sr concentration distribution developed similar characteristics with values ranging from 15 to 64 Bq/m3 under east-southeasterly wind conditions. In addition, in coastal waters, over extensive periods of north-northwesterly winds in 1995, 137Cs concentrations increased to values 1.5-2 times the overall average concentration, which was registered in 1986 and 1996. These data therefore reveal a continuing significant pollution of the waters of the Baltic Sea resulting from the Chernobyl power plant accident, a pollution compounded by the slow rate of radionuclide self-cleaning and significant probability of sudden regional concentration increase.     

The Role of Phytoplankton from the Ob River in Biological Productivity of the Ob–Yenisei Shoal

The program of investigations on the taxonomic composition and spatial distribution of planktonic microalgae in the Gulf of Ob and the southern Kara Sea in different seasons was carried out. Throughout the observation period, from July to October, high values of phytoplankton biomass were recorded in the Gulf of Ob and adjacent areas of the Ob–Yenisei shoal. This is evidence for a higher productivity of waters off the Ob estuary, compared to other coastal areas of the Kara Sea. The main factor responsible for this phenomenon is permanent (during the warm season) transport of living and dead organic matter by river runoff to the shelf.     

The pollution status and the toxicity of surface sediments in Izmit Bay (Marmara Sea), Turkey

Izmit Bay is one of the most polluted and populated enclosed sea in Turkey. It has been the centre of industrial activities for the last 30 years. Seven major sources enter the bay waters along the north coastline of the bay. This investigation forms part of continuing ecotoxicology studies in the Izmit Bay designed to constrain and minimise the pollution caused by flourishing industry and a growing population. Sediments sampled from the mouths of the major discharges of Izmit Bay were analysed for their organic carbon, total polycyclic aromatic hydrocarbon (t-PAH) and trace inorganic element (Cd, Al, As, Pb, Hg and Cu) contents and compared with those found in the sediments from the reference station in the outer bay (in the Marmara Sea). The toxicity of sediments was determined in the bulk and elutriate samples by using algal (Phaeodactylum tricornutum) batch bioassays. Chemical data showed that the sediments collected from the inner sites of the bay have been contaminated with Cd, Hg, As and PAHs. Organic carbon contents were also found higher. All the major industrial discharges into the bay are now biologically treated but bioassays performed with bulk sediments revealed that the recent sediments are toxic to the microalgae throughout the bay. The results are consistent with the previous toxicity studies performed with the industrial discharges.     

Acid-base characteristics of organic carbon in the HUMEX lake Skjervatjern

The Humic Lake Acidification Experiment (HUMEX) was launched in 1988 to study the role of humic substances in the acidification of surface waters and the impacts of acidic deposition on the chemical and biological properties of humic substances. This subproject was designed to determine the contribution of organic acids to the acidity of Lake Skjervatjern (the HUMEX Lake) and the impacts of the acidification on the characteristics of organic carbon. In order to get an empirical measure for organic acidity, dissolved organic carbon (DOC) was fractionated, isolated, and base-titrated from each half of Lake Skjervatjern. Hydrophobic acids were the dominant organic carbon fraction; the total organic acid content was generally greater than 80% of the DOC. The reliability of the fractionation procedure was tested with synthetic acids and the Nordic Fulvic acid. The DOC fractions did not show high variation over the 1.5-y acidification period. Hydrophilic acids had consistently greater exchange acidities compared to hydrophobic acids, averaging 12.9 μeq/mg DOC vs. 10.9 μeq/mg DOC, respectively. The dissociation of organic acids during acid-base titrations clearly increased with increasing pH. The high organic anion contribution to the ion balances indicates that humic matter is an important acidity source in Lake Skjervatjern. There are slight signs that the contribution of organic acids to overall lake acidity has decreased since acidification was initiated.