Photocatalytic degradation of chlorophenols using Ru(bpy) 3 2+ /S2O 8 2−

Advanced oxidation processes, such as photocatalysed oxidation, provide an important route for degradation of wastes. In this study, the lowest excited state (³MLCT) of Ru(bpy)₃²⁺ is used to break down chlorophenol pollutant molecules to harmless products. This has the advantage of using visible light and a short-lived catalytically active species. Photolysis of deaerated aqueous solutions of a variety of mono- and poly-substituted chlorophenols has been followed in the presence of Ru(bpy)₃²⁺/S₂O₈²⁻ with near visible light (λ > 350 nm) by UV/visible absorption spectroscopy, luminescence, potentiometry, NMR and HPLC techniques. Upon irradiation, a decrease is observed in the chlorophenol concentration, accompanied by the formation of Cl⁻, H⁺ and SO₄²⁻ ions as the main inorganic products. Benzoquinone, phenol, dihydroxybenzenes and chlorinated compounds were the dominant organic products. As the ruthenium(II) complex is regenerated in the reaction, the scheme corresponds to an overall catalytic process. The kinetics of the rapid chlorophenol photodechlorination has been studied, and are described quite well by pseudo-first order behaviour. Further studies on this were made by following Cl⁻ release with respect to the initial Ru(bpy)₃²⁺ and S₂O₈²⁻ concentrations. A comparison is presented of the photodechlorination reactivity of the mono and polychlorophenols studied at acidic and alkaline pH.     

Major osmolyte changes during oocyte hydration of a clupeocephalan marine benthophil: Atlantic herring (<Emphasis Type="Italic">Clupea harengus</Emphasis>)

The major inorganic and organic osmolytes responsible for hydrating the oocytes during pre-ovulatory meiotic maturation in autumn- and spring-spawning stocks of Atlantic herring are examined. Despite the ovulated eggs of spring-spawning herring being 1.6- to 2-fold larger than the autumn-spawning stock, the GSI (27 ± 3%) and degree of oocyte hydration (70–72% water) were similar. Normalising the data with respect to dry mass revealed that the physiological mechanisms underlying the maturational influx of water were the same for both classes of egg. Cl⁻, K⁺ and P_i together with a small pool of free amino acids (FAA) represented the driving forces for oocyte hydration. K⁺ (autumn and spring) and P_i (spring) maintained their concentrations in the ovulated eggs, while all other ions, including Cl⁻, Na⁺, NH₄ ⁺ and Mg²⁺ were significantly diluted. In contrast the FAA concentration increased during the hydration process. Amongst the inorganic ions, Cl⁻ showed the greatest increase in the ovulated eggs. The FAA content doubled from 1.5 to 3.3% of dry mass during oocyte hydration and accounted for 29% of the calculated ovoplasmic osmolality in the ovulated eggs from both autumn- and spring-spawners. This significant osmotic effect of the small pool of FAA was due to the low water content of the benthic eggs. The differential movement of the inorganic and organic osmolytes that underly oocyte hydration in Atlantic herring are discussed in relation to current models of transmembrane ion flux.     

Effect of temperature on seawater desalination-water quality analyses for desalinated seawater for its use as drinking and irrigation water

The effect of feed seawater temperature on the quality of product water in a reverse osmosis process was investigated using typical seawater at Urla Bay, Izmir region, Turkey. The tests were carried out at different feed seawater temperatures (11–23°C) using two RO modules with one membrane element each. A number of variables, including pH, conductivity, total dissolved solids, salinity, rejection percentage of a number of ions (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, HCO₃ ⁻, and SO₄ ²⁻), and the levels of boron and turbidities in collected permeates, were measured. The suitability of these permeates as irrigation and drinking water was checked by comparison with water quality standards.     

Effects of water viscosity upon ventilation and metabolism of a flatfish,the common sole <Emphasis Type="Italic">Solea solea</Emphasis> (L.)

The French Atlantic coast contains large highly productive intertidal mudflats that are colonised by juveniles of numerous flatfish species, including the common sole (Solea solea, L.). These ecosystems are also heavily exploited by the shellfish farming industry. Intensive bivalve culture is associated with substantial biodeposition (1–6 t-dw ha⁻¹ day⁻¹), which directly or indirectly contributes to increase exopolysaccharide (EPS) concentrations at the interface between water column and seabed. EPS are long-chain molecules organised into colloids, which influence rheological properties of water, particularly viscosity. Increased water viscosity had consequences for ventilatory activity of juvenile flatfish, whereby the minimal pressure required to ventilate the medium increases directly with EPS concentration. Moreover, the critical EPS concentration ([EPS]_crit) at which water was no longer able to flow through the branchial basket ranged from almost nil to over 30 mg l⁻¹, depending on species and size. [EPS]_crit was lower in small individuals and individuals from species with high metabolic rates (turbot and plaice). These differences may depend upon gill and bucco-branchial cavity morphometrics. The ventilatory workload of sole increased with viscosity to a maximum at 2 mg EPS l⁻¹. Viscosity might, therefore, be a limiting factor for flatfish post larvae, which colonise the intertidal mudflats, depending upon their size and species. EPS concentrations in the field can reach 15 mg l⁻¹. A selective effect is conceivable but remains to be estimated in the field.     

Microsensor studies of photosynthesis and respiration in larger symbiotic foraminifera. I The physico-chemical microenvironment of Marginopora vertebralis, Amphistegina lobifera and Amphisorus hemprichii

 The physico-chemical microenvironment of larger benthic foraminifera was studied with microsensors for O₂, CO₂, pH, Ca²⁺ and scalar irradiance. Under saturating light conditions, the photosynthetic activity of the endosymbiotic algae increased the O₂ up to 183% air saturation and a pH of up to 8.6 was measured at the foraminiferal shell surface. The photosynthetic CO₂ fixation decreased the CO₂ at the shell down to 4.7 μM. In the dark, the respiration of host and symbionts decreased the O₂ level to 91% air saturation and the CO₂ concentration reached up to 12 μM. pH was lowered relative to the ambient seawater pH of 8.2. The endosymbionts responded immediately to changing light conditions, resulting in dynamic changes of O₂, CO₂ and pH at the foraminiferal shell surface during experimentally imposed light–dark cycles. The dynamic concentration changes demonstrated for the first time a fast exchange of metabolic gases through the perforate, hyaline shell of Amphistegina lobifera. A diffusive boundary layer (DBL) limited the solute exchange between the foraminifera and the surrounding water. The DBL reached a thickness of 400–700 μm in stagnant water and was reduced to 100–300 μm under flow conditions. Gross photosynthesis rates were significantly higher under flow conditions (4.7 nmol O₂ cm⁻³ s⁻¹) than in stagnant water (1.6 nmol O₂ cm ⁻³ s⁻¹), whereas net photosynthesis rates were unaffected by flow conditions. The Ca²⁺ microprofiles demonstrated a spatial variation in sites of calcium uptake over the foraminiferal shells. Ca²⁺ gradients at the shell surface showed total Ca²⁺ uptake rates of 0.6 to 4.2 nmol cm⁻² h⁻¹ in A. lobifera and 1.7 to 3.6 nmol cm⁻² h⁻¹ in Marginopora vertebralis. The scattering and reflection of the foraminiferal calcite shell increased the scalar irradiance at the surface up to 205% of the incident irradiance. Transmittance measurements across the calcite shell suggest that the symbionts are shielded from higher light levels, receiving approximately 30% of the incident light for photosynthesis. Received: 6 July 1999 / Accepted: 28 April 2000     

Degradation of carbendazim by UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> investigated by kinetic modelling

The transformation of the fungicide carbendazim (methyl-2 benzimidazole carbamate) induced by hydroxyl radical generated by the UV photolysis of H₂O₂ has been studied in dilute aqueous solution. The efficient reaction of hydroxyl radicals with carbendazim led to the rapid degradation of carbendazim. The study of reaction kinetics yielded a second order rate constant of 2.2±0.3 10⁹ M⁻¹ s⁻¹ for HO^· radicals with carbendazim. This value is in agreement with a high reactivity of HO^· radicals with carbendazim. Most degradation products were identified by high performance liquid chromatography mass spectrometry (HPLC-MS). In the presence of hydrogenocarbonate and carbonate ions, hydroxyl radicals were quenched and in turn carbonate radicals CO₃ ^·− were formed. Carbonate radicals are indeed known to react efficiently with compounds containing electron-rich sites such as nitrogen or sulfur atoms. The use of a kinetic modelling software gave evidence for the occurrence of such reactions with carbendazim. The second order rate constant of carbonate radical with carbendazim was equal to 6±2 10⁶ M⁻¹ s⁻¹. Electronic Publication     

Study on degradation process of famotidine hydrochloride in aqueous samples

The kinetics of famotidine (FAM) transformation under the influence of various factors, important from the environmental point of view, was investigated in aqueous solutions. The degradation processes using UV, H₂O₂, UV/H₂O₂, H₂O₂/Fe²⁺, and UV/H₂O₂/Fe²⁺ were studied. Direct photolysis and H₂O₂-assisted photolysis showed a pseudo-first-order kinetics, while the Fenton and the photo-Fenton processes fit second-order kinetics. The provided experiments proved a high resistance of FAM to direct photolysis. Its stability depends highly on the pH of the reaction solutions. The rate of FAM direct photolysis in acidic solutions was almost negligible. The reaction rate of FAM photolysis at pH 8–9 was 3.7 × 10^?3 min^?1 with DT₅₀ about 3 h 7 min. It was found that the presence of H₂O₂ in the reaction environment enhances the rate of photolysis of FAM. The observed rates of reaction were 5.1 × 10^?3 min^?1 and 3.7 × 10^?3 min^?1 in acidic and basic solutions, respectively. The used Fenton systems appeared to be the most efficient in FAM removal. The rate of reaction depends on concentration of Fe²⁺ and H₂O₂. It was observed that the presence of UV-light enhances the reaction rate by two to six times in comparison to the classical Fenton system. Additionally, FAM behavior in natural water under solar irradiation was examined. The irradiation experiments were carried out in batch experiments with simulated sunlight.     

Photolytical property of L(+)-α-phenylglycine in aqueous solution

A wide range of pharmaceutical compounds have been identified in the environment, and their existence is a topic of growing concern, both for human and ecological health. The work described here has investigated the photolytic properties of L(+)-α-phenylglycine (L-α-PG-H) in aqueous solution as it can be degraded by photo-catalysis. In 266 nm laser flash photolysis of aqueous solution of L-α-PG-H saturated with nitrogen, two transient absorption bands are observed at 280–330 nm and 450–800 nm, respectively, due to L-α-PG-H radical cation and hydrated electrons (e_aq⁻). Then e_aq⁻ reacts with L-α-PG-H to form the L-α-PG-H radical anion. Decaying rate constants of e_aq⁻ observed at 720 nm is to be 8.9 × 10⁸ dm³ mol⁻¹ s⁻¹. The rate constant for oxidation of L-α-PG-H by SO₄ ⁻ is calculated as 4.5 × 10⁸ and 4.3 × 10⁸ s⁻¹ mol⁻¹ dm³, respectively. The dissociation constants (pKa) of L-α-PG-H is 3. Excited triplet of L-α-PG-H in solution is formed by laser flash photolysis. The quench rate constant of L-α-PG-H excited triplet (k _s) is determined to be 1.3 × 10⁷ dm³ mol⁻¹ s⁻¹ and k ₀ is equal to 1.7 × 10⁵ s⁻¹.     

Decrease of Pb bioavailability in solis by addition of phosphate ions

Bioavailability of Pb in contaminated soils can be highly decreased by conversion of labile Pb species into pyromorphite Pb₅(PO₄)₃Cl, induced by amendment with a phosphate source. However, PO₄ ³⁻ can be specifically adsorbed on goethite α-Fe(OH)₃ present in soils. We demonstrate that despite the stability of phosphate ions adsorbed on goethite surface, the reaction between goethite-adsorbed phosphates and aqueous lead in the presence of Cl⁻ results in crystallization of pyromorphite. Two morphological forms of pyromorphite formed on goethite were observed: 1) incrustations, indicating direct reaction of Pb and Cl ions with PO₄ ³⁻ adsorbed on goethite surface, and 2) aggregates of pyromorphite crystals indicating that the reaction with PO₄ ³⁻ ions took place in the volume of the solution. This suggests that precipitation of pyromorphite is faster than desorption of phosphates and that aqueous Pb may serve as a sink for phosphate ions by shifting the equilibrium and inducing PO₄ ³⁻ desorption.     

Aerobic metabolic rates of swimming juvenile mako sharks, <Emphasis Type="Italic">Isurus oxyrinchus</Emphasis>

The shortfin mako shark, Isurus oxyrinchus, is a highly streamlined epipelagic predator that has several anatomical and physiological specializations hypothesized to increase aerobic swimming performance. A large swim-tunnel respirometer was used to measure oxygen consumption (MO₂) in juvenile mako sharks (swimming under controlled temperature and flow conditions) to test the hypothesis that the mako shark has an elevated maintenance metabolism when compared to other sharks of similar size swimming at the same water temperature. Specimen collections were conducted off the coast of southern California, USA (32.94°N and 117.37°W) in 2001-2002 at sea-surface temperatures of 16.0–21.0°C. Swimming MO₂ and tail beat frequency (TBF) were measured for nine mako sharks [77–107 cm in total length (TL) and 4.4 to 9.5 kg body mass] at speeds from 28 to 54 cm s⁻¹ (0.27–0.65 TL s⁻¹) and water temperatures of 16.5–19.5°C. Standard metabolic rate (SMR) was estimated from the extrapolation to 0-velocity of the linear regression through the LogMO₂ and swimming speed data. The estimated LogSMR (±SE) for the pooled data was 2.0937 ± 0.058 or 124 mg O₂ kg⁻¹ h⁻¹. The routine metabolic rate (RMR) calculated from seventeen MO₂ measurements from all specimens, at all test speeds was (mean ± SE) 344 ± 22 mg O₂ kg⁻¹h⁻¹ at 0.44 ± 0.03 TL s⁻¹. The maximum metabolic rate (MMR) measured for any one shark in this study was 541 mg O₂ kg⁻¹h⁻¹ at 54 cm s⁻¹ (0.65 TL s⁻¹). The mean (±SE) TBF for 39 observations of steady swimming at all test speeds was 1.00 ± 0.01 Hz, which agrees with field observations of 1.03 ± 0.03 Hz in four undisturbed free-swimming mako sharks observed during the same time period. These findings suggest that the estimate of SMR for juvenile makos is comparable to that recorded for other similar-sized, ram-ventilating shark species (when corrected for differences in experimental temperature). However, the mako RMR and MMR are apparently among the highest measured for any shark species.     

Assessment of the chemical components of Famenin groundwater,western Iran

The Faminin area in the semi-arid Hamadan state, western Iran is facing a serious deficiency in groundwater resources due to an increasing demand associated with rapid population growth and agricultural development. The chemical composition of 78 well samples throughout the Faminin area was determined with the aim of evaluating the concentration of the background ions and identifying the major hydrogeochemical processes that control the groundwater chemistry. The similarity between rock and groundwater chemistries in the recharge area indicates a significant rock-water interaction. The hydrochemical types Na–HCO₃ and Na–SO₄ are the predominate forms in the groundwater, followed by water types Ca–HCO₃ and Na–Cl. The high values of electrical conductivity and high concentrations of Na⁺, Cl⁻, SO₄²⁻ and NO₃⁻ in the groundwater appeared to be caused by the dissolution of mineral phases and would appeared to be caused by anthropogenic activities, such as intense agricultural practices (application of fertilizers, irrigation practice), urban and industrial waste discharge, among others.     

A convenient and eco-friendly way to synthesize Pt(II) and Pd(II) porphyrins in ionic liquids by microwave activation

Due to the slow rate of incorporation of inert-metal ions into free-base porphyrins compared to other transition metals, several methods have been proposed to accelerate the rate of metalation. However, these methods have disadvantages such as low yields, difficulties of purification of final products, and environmental effects. To avoid those disadvantages, we reacted Pt(II) and Pd(II) salts with H₂(TPP), H₂(TMPyP)⁴⁺, and their β-pyrrole derivatives, H₂(Br₈TPP) and H₂(Br₈TMPyP)⁴⁺, in 1-butyl-3-methylimidazolium bromide ([bmim]⁺Br⁻) under microwave irradiation. The combination of microwave heating and ionic liquids provides efficient thermal energy transfer among the porphyrins and metal salts. In addition, ionic liquids stabilize charged species as well as their intermediates, due to their high dipole moment and high boiling point. This not only shortens the reaction time but also gives high yields of products at relatively low temperatures, of about 100°C compared to conventional synthesis methods: 150°C for DMF, 190°C for DMSO. Here, we demonstrate that Pt(II)/Pt(II) metalloporphyrins are synthesized at high rates, e.g. 6–30 min for 100% metalation, with high yields of 79–93% in [bmim]⁺Br⁻ by microwave activation.     

UV- and salinity-induced oxidative effects in the marine diatom <Emphasis Type="Italic">Cylindrotheca closterium</Emphasis> during simulated emersion

The diatom Cylindrotheca closterium was exposed to transient light- and osmotic conditions as occur during its tidal emersion. The objective was to analyze how this simulated emersion contributes to the production of active oxygen species (AOS) and via this, to oxidative cell damage. Light- and salinity conditions were varied in factorial combination: low light (no UVB) or high light (unweighted UVB-dose rates of respectively 0.01; 0.07; 0.24; 1.03 W m⁻²) at normal (30 psu) or high salinity (60 psu). UVB (0.01–0.24 W m⁻²) and high salinity had a significant, negative effect on the photosynthetic efficiencies ΔF/F _m’ (steady-state quantum yield) and F _v/F _m (maximum yield). UVB at 1.03 W m⁻² (15 kJ m⁻² d⁻¹) almost arrested electron transport. At ecologically relevant UVB levels, i.e. below 0.24 W m⁻² (≈3.4 kJ m⁻² d⁻¹) with UVB:PAR<0.4:100 (PAR photosynthetically active radiation) only dynamic photoinhibition was observed (protection via heat dissipation). Non-photochemical quenching was positively correlated with the de-epoxidation of diadinoxanthin (DD) to diatoxanthin (DT). A decreasing ratio DT/(DD+DT) after 4 h of UVB at >0.07 W m⁻² and at 60 psu indicated a reversal of the diatom xanthophyll cycle (diminished photoprotection) which may be caused by an enhanced AOS production. Oxidative stress and -damage to C. closterium cells were assessed applying fluorescent indicator dyes, via confocal microscopy and quantitative image analysis. AOS production rates (cellular DCF fluorescence) were stimulated by UV, and were ~50% higher at 60 psu. AOS production decreased with an increasing pre-exposure (0–4 h) to normal UVB (0.24 W m⁻²), which indicated a stimulation of the antioxidative defence. Non-protein thiols (indicator CMF) and glutathione pools (HPLC-analyzed) decreased with UVB-dose rates (0.01–0.24 W m⁻²), most likely due to AOS-mediated thiol oxidation. Hypersalinity (60 psu) and UVB (0.01–0.24 W m⁻²) caused membrane depolarization (dye DIBAC₄(3)) and phospholipid hydrolysis (phospholipase A₂ dye: bis-BODIPY FL-C₁₁-PC). AOS production may have diminished the membrane polarity, and peroxidized the membrane lipids (HPLC-analyzed malondialdehyde) which enhanced PLA₂ activity. The dyes indicated an increased oxidative (lipid) damage at a 15% inhibition of photosynthesis in this diatom, at UVB levels and salinities that can be expected in situ during its periodic tidal emersion.     

Osmotic and ionic concentration of the egg capsule fluid of Crepidula fornicata in relation to embryonic development

Osmotic pressure and major ions (Cl⁻, Na⁺, Mg²⁺, Ca²⁺) of the egg capsule fluid in the slipper limpet Crepidula fornicata were investigated in relation to embryonic development. Calcium permeability of the capsule wall was studied at oviposition, by dipping freshly laid egg capsules in ⁴⁵Ca as a tracer. This study also determined total calcium content of the embryos at different developmental stages. Osmolarity and major ion concentrations in egg capsule fluid were higher than seawater at uncleaved and trochophore stages, and then dropped to the same level as sea water at veliger stage. Concentrations of Cl⁻ and Na⁺ were relatively high at oviposition, peaked at trochophore stage, and finally dropped close to concentrations of seawater at hatching. In contrast, concentrations of Mg²⁺ and Ca²⁺ decreased steadily during capsular development. Radiotracer permeability experiments in freshly laid egg capsules confirmed that the capsule wall is impermeable to this ion at that stage. However, because of the dissolution of the inner layer of the wall during the final part of capsular development, the wall becomes permeable to calcium and probably to the rest of the major ions studied.     

Effects of light exposure on the retention of kleptoplastic photosynthetic activity in the sacoglossan mollusc <Emphasis Type="Italic">Elysia viridis</Emphasis>

The effects of light exposure on the photosynthetic activity of kleptoplasts were studied in the sacoglossan mollusc Elysia viridis. The photosynthetic activity of ingested chloroplasts was assessed in vivo by non-destructively measuring photophysiological parameters using pulse amplitude modulation (PAM) fluorometry. Animals kept under starvation were exposed to two contrasting light conditions, 30 μmol photons m⁻² s⁻¹ (low light, LL), and 140 μmol photons m⁻² s⁻¹ (high light, HL), and changes in photosynthetic activity were monitored by measuring the maximum quantum yield of photosystem II (PSII), F _v/F _m, the minimum fluorescence, F _o, related to chlorophyll a content, and by measuring rapid light-response curves (RLC) of relative electron transport rate (rETR). RLCs were characterised by the initial slope of the curve, α_RLC, related to efficiency of light capture, and the maximum rETR level, rETR_m,RLC, determined by the carbon-fixation metabolism. Starvation induced the decrease of all photophysiological parameters. However, the retention of photosynthetic activity (number of days for F _v/F _m > 0), as well as the rate and the patterns of its decrease over time, varied markedly with light exposure. Under HL conditions, a rapid, exponential decrease was observed for F _v/F _m, α_RLC and rETR_m,RLC, F _o not showing any consistent trend of variation, and retention times ranged between 6 and 15 days. These results suggested that the retention of chloroplast functionality is limited by photoinactivation of PSII reaction center protein D1. In contrast, under LL conditions, a slower decrease in all parameters was found, with retention times varying from 15 to 57 days. F _v/F _m, α_RLC and rETR_m,RLC exhibited a bi-phasic pattern composed by a long phase of slow decrease in values followed by a rapid decline, whilst F _o decayed exponentially. These results were interpreted as resulting from lower rates of D1 photoinactivation under low light and from the gradual decrease in carbon provided by photosynthesis due to reduction of functional photosynthetic units.     

Photosynthetic utilisation of inorganic carbon by seagrasses from Zanzibar, East Africa

Photosynthetic rates of eight seagrass species from Zanzibar were limited by the inorganic carbon composition of natural seawater (2.1 mM, mostly in the form of HCO₃ ⁻), and they exhibited more than three time higher rates at inorganic carbon saturation (>6 mM). The intertidal species that grew most shallowly, Halophila ovalis, Halodule wrightii and Cymodocea rotundata, showed the highest affinity for inorganic carbon (K _1/2 = ca. 2.5 mM), followed by the subtidal species (K _1/2 > 5 mM). Photosynthesis of H. wrightii, C. rotundata, Cymodocea serrulata and Enhalus acoroides was >50% inhibited by acetazolamide, a membrane-impermeable inhibitor of carbonic anhydrase, indicating that extracellular HCO₃ ⁻ dehydration is an important part of their inorganic carbon uptake. Photosynthetic rates of H. wrightii, Thalassia hemprichii, Thalassodendron ciliatum, C. serrulata and E. acoroides were strongly reduced by changing the seawater pH from 8.2 to 8.6 in a closed system. In H. ovalis, C. rotundata and Syringodiumisoetifolium, photosynthesis at pH 8.6 was maintained at a higher level than could be caused by the ca. 30% CO₂ concentration which remained in the closed experimental systems at that pH, pointing toward HCO₃ ⁻ uptake in those species. It is suggested that the ability of H. ovalis and C. rotundata to grow in the high, frequently air-exposed, intertidal zone may be related to a capability to take up HCO₃ ⁻ directly, since this is a more efficient way of HCO₃ ⁻ utilisation than extracellular HCO₃ ⁻ dehydration under such conditions. The inability of all species to attain maximal photosynthetic rates under natural conditions of inorganic carbon supports the notion that seagrasses may respond favourably to any future increases in marine CO₂ levels. Received: 19 March 1997 / Accepted: 31 March 1997     

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     

Tracing the factors responsible for arsenic enrichment in groundwater of the middle Gangetic Plain,India: a source identification perspective

Arsenic contamination in groundwater is of increasing concern because of its high toxicity and widespread occurrence. This study is an effort to trace the factors responsible for arsenic enrichment in groundwater of the middle Gangetic Plain of India through major ion chemistry, arsenic speciation, sediment grain-size analyses, and multivariate statistical techniques. The study focuses on the distinction between the contributions of natural weathering and anthropogenic inputs of arsenic with its spatial distribution and seasonal variations in the plain of the state Bihar of India. Thirty-six groundwater and one sediment core samples were collected in the pre-monsoon and post-monsoon seasons. Various graphical plots and statistical analysis were carried out using chemical data to enable hydrochemical evaluation of the aquifer system based on the ionic constituents, water types, hydrochemical facies, and factors controlling groundwater quality. Results suggest that the groundwater is characterized by slightly alkaline pH with moderate to strong reducing nature. The general trend of various ions was found to be Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ > NH₄ ⁺; and HCO₃ ⁻ > Cl⁻ > SO₄ ²⁻ > NO₃ ⁻ > PO₄ ³⁻ > F⁻ in both seasons. Spatial and temporal variations showed a slightly higher arsenic concentration in the pre-monsoon period (118 μg/L) than in the post-monsoon period (114 μg/L). Results of correlation analyses indicate that arsenic contamination is strongly associated with high concentrations of Fe, PO₄ ³⁻, and NH₄ ⁺ but relatively low Mn concentrations. Further, the enrichment of arsenic is more prevalent in the proximity of the Ganges River, indicating that fluvial input is the main source of arsenic. Grain size analyses of sediment core samples revealed clay (fine-grained) strata between 4.5 and 7.5 m deep that govern the vertical distribution of arsenic. The weathering of carbonate and silicate minerals along with surface-groundwater interactions, ion exchange, and anthropogenic activities seem to be the processes governing groundwater contamination, including with arsenic. Although the percentage of wells exceeding the permissible limit (50 μg/L) was less (47%) than that reported in Bangladesh and West Bengal, the percentage contribution of toxic As(III) to total arsenic concentration is quite high (66%). This study is vital considering that groundwater is the exclusive source of drinking water in the region and not only makes situation alarming but also calls for immediate attention.     

Effect of Ca2+ on survival and development of metamorphosing bonefish (Albula sp.) leptocephali

Bonefish (Albula sp.) larvae (leptocephali) from the Gulf of California complete metamorphosis in ˜10 d in natural seawater (35‰S; Ca²⁺ conc = 10.5 mM). The increase in ossification that occurs near the end of the non-feeding metamorphic period, in addition to the ability of larvae to complete metamorphosis in dilute seawater (8‰ S) prompted the present study, where the effects of varying the external calcium ion concentration, [Ca²⁺]_e, of artificial seawater (ASW) on the survival, development and internal (whole-body) calcium ion content, (Ca²⁺)_i, of unfed metamorphosing larvae were investigated. Early-metamorphosing larvae placed in␣ASW, where [Ca²⁺]_e = 10.1 mM, survived for up to 10 d and developed normally without exogenous nutrients. In shorter-term experiments (4 to 5 d), no differences in survival were found for larvae in ASW with [Ca²⁺]_e rang-ing from 1.5 to 10.1 mM. However, in Ca²⁺-free ASW, most larvae died within 27 h and no larvae survived more than 42 h; the median lethal time (LT₅₀), and its 95% confidence limits, were 14.5 (10.0 to 20.9) h. High mortality (81% after 20 h) also occurred in 1.0 mM Ca²⁺ ASW, but 2 of 16 larvae tested survived for 96 h. The 96 h median tolerance limit (TL_M), corrected for control mortality, was 1.2 mM Ca²⁺. In natural seawater, larval (Ca²⁺)_i remained relatively constant ( = 0.419 mg larva⁻¹)␣in early- and intermediate-metamorphosing larvae, and then increased to a mean value of 0.739 mg larva⁻¹ in advanced larvae, indicating that Ca²⁺ was␣taken up from the medium at this stage; the increase in (Ca²⁺)_i corresponded to the period of ossification of the vertebral column. Internal (whole-body) magnesium ion content (Mg²⁺)_i showed no significant change during metamorphosis ( = 0.089 mg larva⁻¹). No significant differences in (Ca²⁺)_i were found in advanced larvae in natural seawater and those in ASW, with [Ca²⁺]_e ranging from 2.0 to 10.1 mM. However, clearing and staining revealed that ossification of the vertebral column had not yet occurred in advanced larvae from 2.0 to 10.1 mM Ca²⁺ ASW. Also, low [Ca²⁺]_e (1.0 to 2.0 mM) usually produced deformed larvae that swam erratically, at times showing “whirling” behavior. Received: 21 August 1996 / Accepted: 26 August 1996