Sequential extraction of cadmium in different soil phases and plant parts from a former industrialized area

Cd concentrations in mobile phases of soil are more representative than total Cd concentration for estimating Cd bioavailability, physicochemical reactivity and mobility. In this study, selective sequential extraction procedures were used to determine Cd in different soil phases. Soil samples and plants grown in these soils were collected from a serpentine and copper-mining area in Maden-Elazig-Turkey. The extracted fractions were exchangeable/carbonate, reducible-iron/manganese oxides, oxidizable-organic matter and sulfides, and residual phases except silicates. Concentrations of Cd in soils and plant samples were determined by flame atomic absorption spectrometry and inductively coupled plasma-mass spectrometry. We found that Cd concentrations in the EDTA and NH₂OH·HCl extracts are higher in most soil samples compared to the other extracts. We conclude that Cd levels in mobile phases are unexpectedly high. The observed Cd concentrations are in ranges of 0.03–3.4 mg kg⁻¹ for soil and 0.02–2.5 mg kg⁻¹ for plant parts. The percentages of cadmium up to 56% in exchangeable and carbonates fractions were observed to be significantly higher than in those values less than 2% reported in literature. This study has shown that the modified extraction method can be usefully applied to determine Cd concentrations in potentially mobile phase of soil. Furthermore, it was concluded that Brassicasea and Rumex leaves can be used as hyperaccumulator plants because their translocation factor and/or enrichment coefficient values were found to be higher than 1.0.     

Fractionation of Heavy Metals in Surface Sediments of Taihu Lake, East China

The BCR (European Communities Bureau of Reference) three-step sequential extraction procedure was applied to fractionate heavy metals in the sediment of Taihu Lake. For the determination of total metal concentration of the sediments, sample digestion was achieved by using HF/H₂O₂/HNO₃(2/1/1) acid mixture in a microwave-irradiated closed vessel system. The concentrations of Cd, Ni, Cr, Zn, Cu and Pb in various extracts solutions were analyzed by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The results obtained from the BCR three-step sequential extraction indicated relatively high mobility of Zn, Cu, Pb and Ni in the sediments while Cd and Cr were poorly mobile. Enrichment of heavy metals was found in the sediments collected in the northern parts of Taihu Lake. In the sediments collected in the southern and western sides of the Lake, heavy metal concentrations were relatively low. The relationship between total organic carbon (TOC) and heavy metals concentrations in the sediments is discussed.     

Mercury contamination in agricultural soils from abandoned metal mines classified by geology and mineralization

Lead (Pb) contents and partition in soils collected from eleven vegetable-growing lands in Fujian Province, China, were investigated using a modification of the BCR (Community Bureau of Reference) sequential extraction procedure coupled with the Pb isotope ratio technique. Pb contents in Chinese white cabbage (B. Chinensis L.) grown on the lands for this study were also measured. Results showed that Pb concentrations in fifty samples of topsoil ranged from 456 to 21.5 mg kg⁻¹, with each mean concentration of six sampling lands exceeding the national standard (50 mg kg⁻¹); while Pb concentrations in edible portions of thirty-two vegetable samples ranged from 0.009 to 2.20 mg kg⁻¹, with four sampling sites exceeding the national sanitary standard (0.2 mg kg⁻¹). A significant correlation (r = 0.971, P < 0.01) of Pb contents in the acid-extractable fractions by BCR approach and the vegetables was observed, which indicates that the acid-extractable Pb is useful for evaluating the metal bioavailability for plants and potential risk for human health in soils. The determination of lead isotope ratios in different chemical forms of soils by BCR sequential extraction procedures provides useful information on the Pb isotopic composition associated with different soil fractions (especially in the acid-extractable fractions), and the result is helpful for the further study on controlling and reducing Pb contamination in vegetable-growing soils.     

Geochemical Distribution and Bioavailability of Heavy Metals and Oxalate in Street Sediments from Rio de Janeiro, Brazil: A Preliminary Investigation

As urbanisation accelerates within less-economically developed countries, populations in cities such as Rio de Janeiro are subject to numerous health risks relating to “heavy metal”, sewage and vehicle pollution. These risks apply especially to children, through inhalation and dermal contact with pollutant-rich street sediments that reflect contamination from atmospheric deposition and act as effective sinks for heavy metals and oxalates. To assess the nature and extent of these risks street sediments were collected from industrial, commercial, residential and recreational areas with varying traffic densities within Rio de Janeiro. A modified selective extraction procedure was used to study the geochemical partitioning and bioavailability of Fe, Mn, Zn, Cu, Cr, Ni, Pb and C₂O ₄ ⁻ . Oxalate partitioning has not been studied by traditional sequential methods and results from this procedure highlight the potential bioavailability of both oxalates and “heavy metals”, especially Pb and C₂O ₄ ⁻ in industrial and recreational areas.     

Uranium speciation in river sediments contaminated by phosphate ores

Large amounts of phosphate ores with high concentrations of uranium were dumped by a phosphate plant into the Flix water reservoir in the Ebre River, Catalonia, NE Spain. These phosphate wastes have been mixed over the years with effluents from other industries as well as with the sediments of the river, resulting in a complex mixture of solid wastes and sediments. No investigations on uranium speciation in such sediments were made because of the complexity of the sediments composition as well as the relatively low uranium content. However, these studies are necessary in order to predict the release of the uranium to the river waters. Here, we studied uranium speciation in sediments from two sampling points of the Flix water reservoir and at depths from 5 to 113 cm. We used room temperature time-resolved laser fluorescence spectroscopy and a three-step sequential extraction procedure described by the Standards, Measurements, and Testing Programme of the European Union. We found that uranium was mainly present in the sediment samples as meta-autunite [Ca(UO₂)₂(PO₄)₂·10–12H₂O], whose low solubility will result in a low release of uranium to the river waters. In addition, we found that some uranium was linked to sediments by forming surface complexes. We therefore made the first study of uranium speciation in the sediments of the Flix water reservoir.     

A Petrographic Investigation of two Sequential Extraction Techniques Applied to Anaerobic Canal Bed Mud

The application of sequential extraction procedures to determine metal speciation in sediments is fraught with uncertainty regarding what is actually dissolving or re-precipitating at each stage. In order to choose an appropriate scheme for the investigation of contaminated anaerobic mud two different sequential extraction procedures (Kersten and Förstner, 1986; Quevauviller, 1998) were investigated using a Cryogenic SEM (CryoSEM) technique coupled with energy dispersive X-ray analysis (EDXA). This enabled assessment of the degree of reagent selectivity and any re-precipitation associated with the respective methods. Analysis of the non-leached sediment revealed the most abundant authigenic minerals in order of decreasing abundance to be Fe²⁺-phosphate vivianite (Fe₃(PO₄)₂·8H₂O), mixed Fe, Zn, Cu sulphides, pyrite and calcite. After each stage of the sequential extraction the sediment residue was examined using CryoSEM. After extraction of the exchangeable fraction no obvious evidence of mineral dissolution was observed. Calcite was not completely dissolved during the carbonate extraction stage of either procedure. Vivianite began to dissolve in the carbonate extraction stage of both procedures and was completely dissolved by oxide extraction stage of both procedures. The sediment leached by acidified ammonium oxalate, contained abundant Fe oxalate crystals, suggesting that a large proportion of the Fe released from the vivianite has been re-precipitated. The Fe oxalate was then dissolved with the subsequent sulphide fraction. The technique used to extract the sulphide and organic fraction is the same in both schemes and no sulphide or metal rich organic matter was found in either residue.     

Fractionation of heavy metals in surface sediments of Taihu Lake, East China

The BCR (European Communities Bureau of Reference) three-step sequential extraction procedure was applied to fractionate heavy metals in the sediment of Taihu Lake. For the determination of total metal concentration of the sediments, sample digestion was achieved by using HF/H2O2/HNO3 (2/1/1) acid mixture in a microwave-irradiated closed vessel system. The concentrations of Cd, Ni, Cr, Zn, Cu and Pb in various extracts solutions were analyzed by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The results obtained from the BCR three-step sequential extraction indicated relatively high mobility of Zn, Cu, Pb and Ni in the sediments while Cd and Cr were poorly mobile. Enrichment of heavy metals was found in the sediments collected in the northern parts of Taihu Lake. In the sediments collected in the southern and western sides of the Lake, heavy metal concentrations were relatively low. The relationship between total organic carbon (TOC) and heavy metals concentrations in the sediments is discussed.     

Unexpected toxicity decrease during photoelectrochemical degradation of atrazine with NaCl

This report shows an unexpected toxicity decrease during atrazine photoelectrodegradation in the presence of NaCl. Atrazine is a pesticide classified as endocrine disruptor occurring in industrial effluents and agricultural wastewaters. We therefore studied the effects of the degradation method, electrochemical and electrochemical photo-assisted, and of the supporting electrolyte, NaCl and Na₂SO₄, on the residual toxicity of treated atrazine solutions. We also studied the toxicity of treated atrazine solutions using Artemia nauplii. Results show that at initial concentration of 20 mg L⁻¹, atrazine was completely removed in up to 30 min using 10 mA cm⁻² electrolysis in NaCl medium, regardless of the electrochemical method used. The total organic carbon removal by the photo-assisted method was 82% with NaCl and 95% with Na₂SO₄. The solution toxicity increased during sole electrochemical treatment in NaCl, as expected. However, the toxicity unexpectedly decreased using the photo-assisted method. This finding is a major discovery because electrochemical treatment with NaCl usually leads to the formation of toxic chlorine-containing organic degradation by-products.     

Concentrations of inorganic elements in bottled waters on the Swedish market

This study presents the concentrations of about 50 metals and ions in 33 different brands of bottled waters on the Swedish market. Ten of the brands showed calcium (Ca) concentrations ≤10 mg L⁻¹ and magnesium (Mg) levels <3 mg L⁻¹, implying very soft waters. Three of these waters had in addition low concentrations of sodium (Na; <7 mg L⁻¹), potassium (K; <3 mg L⁻¹) and bicarbonate (HCO₃ ≤31 mg L⁻¹). These brands were collected from barren districts. Nine of the brands were collected from limestone regions. They showed increased Ca-levels exceeding 50 mg L⁻¹ with a maximum of 289 mg L⁻¹. Corresponding Mg-levels were also raised in two brands exceeding 90 mg L⁻¹. Two soft and carbonated waters were supplemented with Na₂CO₃ and NaCl, resulting in high concentrations of Na (644 and 648 mg L⁻¹) and chloride (Cl; 204 and 219 mg L⁻¹). Such waters may make a substantial contribution to the daily intake of NaCl in high water consumers. The storage of carbonated drinking water in aluminum (Al) cans increased the Al-concentration to about 70 μg L⁻¹. Conclusion As there was a large variation in the material as regards concentrations of macro-elements such as Ca, Mg, Na, K and Cl. Supplementation with salts, e.g., Na₂CO₃, K₂ CO₃ and NaCl, can lead to increased concentrations of Na, K and Cl, as well as decreased ratios of Ca/Na and larger ratios of Na/K. Water with high concentrations of e.g., Ca and Mg, may make a substantial contribution to the daily intake of these elements in high water consumers. Al cans are less suited for storage of carbonated waters, as the lowered pH-values may dissolve Al. The levels of potentially toxic metals in the studied brands were generally low.     

Changes in chemical forms of lead in temperate and semiarid soils in sterile and unsterile conditions

Sequential extraction has been used as a suitable method for fractionation of chemical forms of trace elements and study of their plant availability. Surface soils were sampled from Guilan and Hamadan provinces in north and northwest of Iran with temperate and semiarid climates. The chemical forms of Pb in the Pb(NO₃)₂-treated (400 μg Pb g⁻¹) soils have been studied in solid state incubation (FC) at 27°C in sterile and unsterile conditions. After 20 min and 3600 h a sequential extraction scheme was also used to fractionate Pb of incubated samples into soluble-exchangeable (Sol-Exch), carbonates associated (ACar), organic matter associated (AOM), Mn oxide associated (AMnOx), Fe oxide associated (AFeOx), and residual (Res) forms. Temperate soil samples had higher clay content, cation exchange capacity (CEC), dichromate oxidable organic carbon (OC), total Kjeldahl-nitrogen (TN), biological activity, amorphous and crystalline Fe and Al, but semiarid soil samples had higher sand content, pH, equivalent calcium carbonate (ECC), available P and K. Soil lead fractionation revealed that in both groups of soils Pb largely changed to exchangeable, carbonates associated and organic associated forms after 20 min. The chemical forms of Pb differed widely among soils after 3600-h incubation. The conversion rate of Pb from more available forms to less available forms was higher in temperate soils with higher Fe–Mn oxides and OM contents compared to semiarid soils. In temperate soils after 3600-h incubation, greater content of Pb was observed in Res (68%), AOM (14%), ACar (7%), and AMnOx (5%) fractions. However, in semiarid soils greater content of Pb was observed in Res (61%), ACar (16%), Sol-Exch (8%), and AOM (8%) fractions. The sum of AMnOx and AFeOx chemical forms for Pb in semiarid soils compared to temperate soils was lower. It was only 7% against 9% in temperate soils. Soil microorganisms in unsterile soils had significant effect on AOM, AFeOx and Res fractions of Pb. They not only increased AOM and AFeOx fractions of Pb in soils but also decreased Res fraction of Pb significantly.     

The chemistry of aluminum in the environment

There is increased concern over the effects of elevated concentrations of Al in the environment. Unfortunately, studies of the environmental chemistry and toxicity of Al have been limited by our understanding of the processes regulating the aqueous concentration, speciation and bioavailability of this element.Although Al is the most abundant metallic element in the Earth's crust, it is highly insoluble and generally unavailable to participate in biogeochemical reactions. However, under highly acidic or alkaline conditions, or in the presence of complexing ligands, elevated concentrations may be mobilized to the aquatic environment. Ecologically significant concentrations of Al have been reported in surface waters draining acid-sensitive regions that are receiving elevated inputs of acidic deposition. Acid- sensitive watersheds are characterized by limited release of basic cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) and/or retention of strong acid anions (SO₄ ^2–, NO₃ ^–, Cl^–). Under these conditions inputs of strong acids are not completely neutralized, but rather acidic water is exported from the terrestrial environment. It has been hypothesized that acidic deposition to acid-sensitive watersheds mobilizes Al within the mineral soil, causing elevated concentrations in soil solutions and surface waters. As a result of mineral phase solubility constraints, concentrations of aqueous Al increase exponentially with decreases in pH below 6.0.Monomeric Al occurs as a series of complexes in the aqueous environment, including aquo, OH^–, F^–, SO₄ ^2–, HCO₃ ^– and organic species. Of these aquo, OH^–, F^– and organic complexes are the most significant in natural waters.Elevated concentrations of Al are ecologically significant because: 1) Al is an important pH buffer in acidic waters, regulating the lower limit of pH values following acidification by strong acids; 2) through adsorption and coagulation reactions, Al may alter the cycling and availability of important elements like phosphorus, organic carbon and certain trace metals; 3) Al may serve as a coagulant facilitating the removal of light attenuating materials, thereby increasing the clarity and decreasing the thermal stability of lakes; and 4) Al is potentially toxic to organisms. Better understanding of the chemistry and speciation of Al is essential to assess these effects.     

Toxizität von Aluminium

The concentration of solubilized aluminium in soils and waters increases due to environmental influences. To obtain information on the types of Al species occuring under these conditions, aluminium chloride solutions were prepared in a wide range of concentrations (10^?1–10^?5 mol·l^?1 Al) and basicity (OH/Al=0,5–2,5), respectively, and then structurally characterized using the ferron method. For the freshly prepared solutions, a decrease in the portion of monomeric Al species is observed, with an increasing OH/Al-ratio; the formation of polymeric cations decreases to lower OH/Al-ratios with diminishing concentration. The portion of tridecameric cations (Al₁₃) decreases with diminishing concentration, but so called transition polymers occur in these solutions. The transition polymers are instable under ageing; by inreasing the ageing time, a disproportion of these cations into monomeric and polymeric species can be observed. At extremly low Al concentrations (10^?5 mol·l^?1 Al), a condensation of the transition polymers into polymeric species occurs, after only a short ageing. The influence of admixtures of Mg²⁺-and Ca²⁺-ions, respectively, on the specification of the Al cations are only observed after longer ageing times; in this case, the formation of polymeric Al species is forced. The polymeric Al species therefore, seem to be especially preferred alongside the monomeric ones under biologically relevant concentrations.     

Branchial and intestinal osmoregulatory acclimation in the four-eyed sleeper, <Emphasis Type="Italic">Bostrychus sinensis</Emphasis> (Lacepède), exposed to seawater

Bostrychus sinensis is a facultative air breather that inhabits waters of a wide range of salinities. This study aimed to elucidate whether branchial and intestinal osmoregulatory acclimation occurred in B. sinensis transferred from 5‰ water through a progressive increase in salinities to seawater. Our results indicate that B. sinensis acted as a hyperosmotic regulator in 5‰ water, but exhibited hypoosmotic hypoionic regulation in seawater. During short- (1 day) and medium- (10 days) term acclimation to seawater, there were only minor perturbations in plasma osmolality and [Na⁺], which returned to control levels after 45 days of exposure to seawater. Branchial Na⁺/K⁺-ATPase activity was unaffected by 1, 10 or 45 days of exposure to seawater. However, prolonged (45 days) acclimation to seawater led to a significant increase in Na⁺/K⁺-ATPase α-subunit protein abundance. Taken together, these results indicate that there could be changes in the expression of Na⁺/K⁺-ATPase isoforms and/or post-translational modification of Na⁺/K⁺-ATPase in the gills of fish exposed to seawater. Immunofluorescence microscopy revealed that acclimation to seawater for 10 days only resulted in no change in branchial Na⁺/K⁺-ATPase protein expression, but there were increases in protein expression of cystic fibrosis transmembrane regulator (CFTR)-like chloride channel and Na⁺:K⁺:2Cl⁻ cotransporter (NKCC; probably NKCC1). Indeed, NKCC was undetectable in gills of fish kept in 5‰ water by Western blotting, but it became weakly detectable in fish exposed to seawater for 10 days and prominently expressed in fish exposed to seawater for 45 days. Therefore, our results indicate that branchial CFTR-like chloride channel and NKCC1 were the determining factors in the transition between hyperosmotic regulation and hypoosmotic hypoionic regulation in B. sinensis. Furthermore, the intestine of B. sinensis also served as an important osmoregulatory organ, since there were significant increases in both the activity and protein abundance of intestinal Na⁺/K⁺-ATPase in fish acclimated to seawater for 45 days. The effectiveness of branchial and intestinal osmoregulatory acclimation in B. sinensis during seawater acclimation led to only a minor increase in plasma osmolality, and thus resulted in relatively unchanged free amino acid contents in muscle and liver.     

Remobilization of selected metal ions from Nile sediment (Egypt) according to sequential extraction and metal–EDTA complex

River sediments are basic components of our environment, providing nutrients for living organisms and serving as sinks for deleterious chemical species. The metal contents may be remobilized and released back into waters with changes in environmental conditions, thus affecting living organisms and human activities. This paper aims to determine the effect of a synthetic anthropogenic chelating agent (EDTA) as industrial discharges on the remobilization of several metals (Cu, Zn, Cd, and Pb) in River Nile sediments (at Aswan and Mansoura cities) under different concentrations and pH values, and to investigate the influence of metal–EDTA complexes on this remobilization. For these purposes, sequential extraction and experiments on the effect of pH and metal EDTA complex were carried out on the two representative sediment samples south and north of the River Nile in Egypt. The results of sequential extraction show that most of metal contents present in the residual form (Cu, 11.36–72.34%; Pb, 29.64–66.67%; and Zn, 43.76–50.09% at Aswan and Mansoura, respectively). Non-residual fractions which may be available for the remobilization by EDTA represented anthropogenic (industrial, agriculture, and domestic discharges) and lithiopogenic (metals bound to Fe and Mn oxides) sources. A clear increase was detected for Cu and Zn remobilization from the increase in EDTA concentrations, in contrast, Cd independent of the EDTA concentration and slight influence on Pb content. The remobilization of metals as a function of pH exhibited. The metals were greatly remobilized under the complexing action of EDTA, showing that some of these elements were adsorbed on the sediments. The remobilization rate of metals was dependent upon the added metal–EDTA complex (with the exchange rate being in the order Ca–EDTA>Zn–EDTA>Cd–EDTA>Cu–EDTA>Pb–EDTA), due to the stability constant of the metal–EDTA complex. The results of these experiments showed that heavy metals are greatly remobilized under the complexing action of EDTA when it is present in excess, so all precautions should be taken to prevent any wastewater containing EDTA or any chelating agents discharging directly or indirectly via the River Nile stream because most EDTA remains in the aquatic phase. The ability of this portion to remobilize metals from sediments should be taken into account.     

Simulating the dynamics of sulfur species and zinc in wetland sediments

In situ measurements comparing vertical SO₄²⁻ profiles in vegetated and non-vegetated sediments showed that SO₄²⁻ concentrations in vegetated sediments increased significantly at the beginning of the growing season and then gradually decreased during the rest of the growing season. Throughout the growing season, SO₄²⁻ concentrations remained higher in the vegetated sediments than in the sediments without plants. The higher SO₄²⁻ concentrations in the vegetated sediments indicate that oxygen release from roots and evapotranspiration-induced advection by plants play an important role in the dynamics of sulfur species in sediments. Since the total pool of solid-phase sulfide is relatively large compared to the mass of SO₄²⁻ in the sediments, the gradual decrease of SO₄²⁻ concentrations may result from limitation of the solid-phase sulfide that is in direct contact with or very close to the roots and rhizomes. This would mean that the main pool of solid-phase sulfide and associated trace metals are not affected by the oxygen release from roots, and the associated trace metals will not become bioavailable during the growing season.     

The hydrolytic products of aluminum and their biological significance

The relative distribution of Al between its various organic and inorganic complexes dictates its mobility in the environment, bioavailability, and toxicity. In recent years, there has been significant progress made in understanding the differential bioavailability and toxicity of various chemical species of Al to plants and certain aquatic organisms. Far less information concerning chemical speciation and differential uptake and transport of Al in humans is available. Among the important inorganic complexes of interest are the hydrolyzed-Al species, particularly the nonequilibrium, metastable polynuclear complexes, which form readily, have a fairly wide stability range, and have been demonstrated toxic to plants and fish. In recent years²⁷Al NMR spectroscopy has provided significant direct information on the polynuclear complexes existing in a wide range of aqueous solutions. The [Al₁₂O₄(OH)_24+n(H₂O)_12–n]^(7–n)+ polynuclear complex is often found to be the predominant species in partially neutralized Al solutions and has recently been demonstrated to be more toxic to certain plants than the hexaaqua Al cation. It is also the principal component of Al-chlorohydrate, a highly soluble antiperspirant, present in many hydrolyzed Al solutions utilized in water and waste water treatment, and, as hypothesized herein, a primary constituent of many hydroxide gels utilized as antacids. This polynuclear has a wide pH stability range, reportedly forms copolynuclears with Si, and contains tetrahedrally coordinated Al within its structure, all features that may be relevant to the recently reported properties of Al associated with neuritic plaque cores.     

Geochemistry and quality of groundwater of the Yarmouk basin aquifer,north Jordan

Quality of groundwater in the Yarmouk basin, Jordan has been assessed through the study of hydrogeochemical characteristics and the water chemistry as it is considered the main source for drinking and agriculture activities in the region. The results of the relationship between Ca²⁺ + Mg²⁺ versus HCO₃^? + CO₃^2?, Ca²⁺ + Mg²⁺ versus total cations, Na⁺ + K⁺ versus total cations, Cl^? + SO₄^2? versus Na⁺ + K⁺, Na⁺ versus Cl^?, Na⁺ versus HCO₃^? + CO₃^2?, Na⁺ versus Ca²⁺, and Na⁺: Cl^? versus EC describe the mineral dissolution mechanism through the strong relationship between water with rocks in alkaline conditions with the release of Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃^?, CO₃^2?, SO₄^2?, and F^? ions in the groundwater for enrichment. Furthermore, evaporation processes, groundwater depletion, and ion exchange contribute to the increased concentration of Na⁺ and Cl^? ions in groundwater. Anthropogenic sources are one of the main reasons for contamination of groundwater in the study area and for increasing the concentration of Mg²⁺, Na⁺, Cl^?, SO₄^2?, and NO₃^? ions. Results show the quality of groundwater in the study area is categorized as follows: HCO₃^? + CO₃^2? > Cl^? > SO₄^2? > NO₃^? > F^? and Na⁺ > Ca²⁺ > Mg²⁺ > K⁺. In conclusion, the results of TDS, TH, and chemical composition showed that 26% of the groundwater samples were unsuitable for drinking. About 28% of groundwater samples in the study area have a high concentration of Mg²⁺, Na⁺, and NO₃^? above the acceptable limit. Also, based on high SAR, 10% of the groundwater samples were not suitable for irrigation purposes.     

Aluminium in tea plantations: mobility in soils and plants, and the influence of nitrogen fertilization

The levels of extractable aluminum (Al) in soils of tea plantations, Al concentrations in tea leaves and the impact of nitrogen fertilization on these two parameters were investigated. In addition, the properties of soils from tea plantations were compared to those from soils of adjacent non-tea fields to evaluate the effect of land use conversion (from non-tea soils to tea soils). Exchangeable Al (extracted in 1 mol l⁻¹ KCl) ranged from 0.03 to 7.32 cmol_c kg⁻¹ in 94 tea fields and decreased rapidly with increasing soil pH. In comparison with non-tea soils, tea soils had a significantly lower pH and exchangeable Mg²⁺ concentration but higher organic matter contents and exchangeable K⁺ concentration. Contents of extractable Al were not different (P > 0.05) between these two soils. The concentrations of Al in mature tea leaves correlated significantly with exchangeable Al in soil samples taken at a depth of 20–40 cm and with exchangeable Al saturations in soil sampled at␣depths of 0–20 and 20–40 cm. In the pot experiment, nitrogen fertilization significantly increased extractable Al levels but decreased soil pH and the levels of exchangeable base cations. Nevertheless, the levels of Al in mature leaves and young shoots were significantly reduced by the application of large amounts of N fertilizer.     

Inhibition of Na+/K+-ATPase and of active ion-transport functions in the gills of the shore crab Carcinus maenas induced by cadmium

Inhibition of Na⁺/K⁺-ATPase from gill plasma membranes of the shore crab Carcinus maenas by cadmium was investigated and compared with inhibitory effects by known antagonists (ouabain and Ca²⁺). For comparative considerations the Cd²⁺-inhibition of the enzyme from dog kidney was also tested. Na⁺/K⁺-ATPase from dog kidney and from crab gill differed greatly in sensitivity against ouabain. The inhibition constant K _i of the dog enzyme amounted to 9.1 × 10⁻⁷ mol l⁻¹, i.e. more than 300-fold smaller than the K _i of 2.9 × 10⁻⁴ mol l⁻¹ determined for the crab enzyme. Ca²⁺ inhibited the activity of Na⁺/K⁺-ATPase from crab gill plasma membranes with a K _i of 4.3 × 10⁻⁴ mol l⁻¹. The Na⁺/K⁺-ATPase from crab gill was inhibited by Cd²⁺ with a K _i of 9.1 × 10⁻⁵ mol l⁻¹. Cd²⁺ inhibited the Na⁺/K⁺-ATPase from dog kidney with a K _i (6.4 × 10⁻⁵ mol l⁻¹) comparable to that observed in the crab gill enzyme. Under experimental conditions Cd²⁺-inhibition of Na⁺/K⁺-ATPase was irreversible. Repeated washing, centrifugation and homogenization of the plasma membranes (four times) with Cd²⁺-free buffer did not restore any activity lost in the presence of 1 × 10⁻³ mol l⁻¹ Cd²⁺. Since ouabain-insensitive (nonspecific) ATPases in the plasma membrane fraction of crab gills were inhibited by Cd²⁺ in the same way as Na⁺/K⁺-ATPase, the heavy metal is considered as an unspecific ATPase inhibitor. Comparing these results with literature data on Cd²⁺-binding to electrophoretically separated proteins suggests that Na⁺/K⁺-ATPase is a Cd²⁺-binding enzyme. The results obtained on Na⁺/K⁺-ATPase were reflected by Cd²⁺-inhibition of the branchial ion-transport functions depending on this enzyme. The transepithelial short-circuit current of isolated gill half lamellae, a direct measure of area-specific active ion uptake, and the transepithelial potential difference of isolated, perfused whole gills, also indicative of active ion uptake, were inhibited by the heavy metal in a time- and dose-dependent mode. Remarkably these inhibitions were also irreversible. These findings are ecologically and biomedically significant: even when the actual environmental or tissue concentrations measured are low, biological microstructures such as Na⁺/K⁺-ATPase may accumulate the heavy metal by tight binding over prolonged periods until the first inhibitory effects occur. Received: 25 June 1997 / Accepted: 25 August 1997