Ferrate(VI) oxidation of ibuprofen: A kinetic study

The kinetics of ferrate(VI) (Fe^VIO₄ ²⁻, Fe(VI)) oxidation of an antiphlogistic drug, ibuprofen (IBP), as a function of pH (7.75–9.10) and temperature (25–45°C) were investigated to see the applicability of Fe(VI) in removing this drug from water. The rates decrease with an increase in pH and the rates are related to protonation of ferrate(VI). The rates increase with an increase in temperature. The E _a of the reaction at pH 9.10 was calculated as 65.4±6.4 kJ mol⁻¹. The rate constant of the HFeO₄ ⁻ with ibuprofen is lower than with the sulphur drug, sulfamethoxazole. The use of Fe(VI) to remove ibuprofen is briefly discussed.     

Population biology and life strategies of Chlorophthalmus agassizii Bonaparte, 1840 (Pisces: Osteichthyes) in the Mediterranean Sea

The population biology and life strategies of Chlorophthalmus agassizii were studied in the Ionian Sea (eastern–central Mediterranean) using the data collected during the experimental trawl surveys carried out from 1995 to 2000. Depth-related trends of both density and size were found. With depth the former decreased while the latter increased. A typical bigger–deeper phenomenon was detected: young-of-the-year individuals occur on the shelf during autumn–winter months and move towards bathyal bottoms as they grow. The sampled population was made up of several size–age groups. The maximum age of 8 years was identified by means of otolith readings. The Von Bertalanffy growth parameters were estimated from the age–length key (L _∞=189.04±5.401 mm; k=0.24±0.021; t _o=−1.20±0.132; φ′=3.94) and modal progression analysis (L _∞=218.33±18.397 mm; k=0.164±0.028; t _o=−1.694±0.171; φ′=3.89). Reproduction of this monoecious fish was observed during summer–early autumn. Considering the female portion of the gonad, the size at attainment of 50% maturity was 115 mm TL. The corresponding age is within the third year of life. The simultaneous occurrence of oocytes in different development stages was shown in the ovary. Both the asynchronous ovary and oocyte size distribution indicate that C. agassizii spawns more than once during a reproductive season (batch spawner). Functional fecundity (on average 3,018 hydrated oocytes) was between 37 and 69% of the absolute fecundity and increased significantly with the individual size. Since adult specimens are mostly distributed on the slope, eggs and larvae develop in epipelagic waters and migrate in-shore where juvenile forms recruit on the shelf. Juveniles migrate ontogenetically towards deeper bottoms and after 2–3 years start to reproduce annually within a life span greater than 10 years.     

Concentrations of inorganic elements in 20 municipal waters in Sweden before and after treatment – links to human health

The water chemistry of 20 municipal water treatment plants in southern Sweden, representing various bedrock situations, and water qualities, were investigated. Four water samples, raw and treated, were collected from each plant and analyzed by predominantly ICP-OES and ICP-MS at four occasions from June to December, 2001. The concentrations of Ca, Mg, K, Na, HCO₃ and a number of micronutrients, varied considerably in treated waters from the studied plants (ranges; Ca: 9.1–53.7 mg L⁻¹, Mg: 1.4–10.9 mg L⁻¹, K: 1.1–4.8 mg L⁻¹, Na; 5.4–75.6 mg L⁻¹, HCO₃: 27–217 mg L⁻¹). The elimination of Fe and Mn from raw water was efficient in all treatments investigated, giving concentrations in treated waters below the detection limits at some plants. Softening filters gave waters with Ca-concentrations comparable to the softest waters in this study. Adjustment of pH by use of chemicals like lye, soda or lime, modified the consumer water composition significantly, besides raising the pH. It was estimated that drinking water contributed to approximately 2.2–13% of the daily Ca uptake, if the gastrointestinal uptake efficiency from food and water was estimated to be around 50%. The corresponding figures for Mg was 1.0–7% and for F 0–59%. None of the studied elements showed any significant time trends in raw or treated waters during the follow-up period. The concentrations of potentially toxic metals such as Al, Pb and U were low and did not indicate risks for adverse health effects (ranges; Al: 0.5–2.3 μg L⁻¹, Pb: 0–0.3 μg L⁻¹, U: 0.2.5 μg L⁻¹).     

Extraction of Co,Ni, Cu,Zn and Cd ions using 2-aminophenylaminopropylpolysiloxane

Insoluble porous solid functionalized ligand system bearing 2-aminophenylaminopropyl chelating ligand of the general formula P–(CH₂)₃NH–(C₆H₄)–NH₂ was prepared via the sol–gel process, where P represents [Si–O] _n polysiloxane network. First, the 2-aminophenylaminopropylsilane agent was prepared by substitution reaction between 3-chloropropyltrimethoxysilane and 1,2-phenylenediamine, followed by hydrolytic polycondensation between 2-aminophenylaminopropylsilane agent and tetraethylorthosilicate(TEOS). The immobilized 2-aminophenylaminopropylpolysiloxane P–(CH₂)₃NH–(C₆H₄)–NH₂(P–AphA) was characterized by ¹³C NMR, XPS, and FTIR. The results showed that 1,2-phenylenediamine groups were introduced onto polysiloxane network. The functionalized ligand system exhibits 90–100% metal uptake capacity for all metal ions except Cd²⁺. The elemental analysis data and the metal uptake capacities of the immobilized ligand system suggest that over than 90% ligand sites were involved in coordination with metal ions except that of cadmium forming 1:1 metal to ligand ratio complexes.     

Life on the edge: physiological problems in penaeid prawns <Emphasis Type="Italic">Litopenaeus stylirostris</Emphasis>, living on the low side of their thermopreferendum

The underlying physiological mechanisms explaining why the adult penaeid prawn Litopenaeus stylirostris cannot successfully face heavy stressful events on the low edge of its thermopreferendum (20–22°C) were studied during the austral winter. Prawns were studied during recovery from net fishing and rapid transfer from outdoor earthen ponds into indoor facilities. This was assimilated to a predator–prey interaction. O₂-consumption, hemolymph osmotic pressure (OP_h), arterial O₂ partial pressure (PO₂), a–v O₂-capacitance and mortality rates were analysed. Data were compared to similar challenges performed at 28°C during the austral summer. At 20–22°C, mortality of up to 70% was observed after 2 days whereas at 28°C, maximum mortality was 3–5%. Mortality occurred when OP_h shifted towards equilibrium with seawater, the resting O₂-consumption, the a–v O₂-capacitance and the arterial PO₂ went down to minimal values. These events can be counterbalanced by transiently hyper-oxygenating the hemolymph or by blocking the OP_h shift in isosmotic water (Wabete et al. in Aquaculture 260:181–193, 2006): both led to a dramatic decrease in mortality. It is concluded that in penaeid prawns L. stylirostris, a mismatch between O₂-demand and O₂-supply contributes to setting the geographical limits for this animal species through an impairment of their hemolymph O₂-carrying capacity during heavy stressful events like chasing by predators.     

Biomineralogy of human urinary calculi (kidney stones) from some geographic regions of Sri Lanka

Kidney stones (urinary calculi) have become a global scourge since it has been recognized as one of the most painful medical problems. Primary causative factors for the formation of these stones are not clearly understood, though they are suspected to have a direct relationship to the composition of urine, which is mainly governed by diet and drinking water. Sixty nine urinary calculi samples which were collected from stone removal surgeries were analyzed chemically for their Na, K, Ca, Mg, Cu, Zn, Pb, Fe and phosphate contents. Structural and mineralogical properties of stones were studied by XRD and FT-IR methods. The mean contents of trace elements were 1348 mg kg⁻¹ (Na); 294 mg kg⁻¹ (K); 32% (Ca); 1426 mg kg⁻¹ (Mg); 8.39 mg kg⁻¹ (Mn); 258 mg kg⁻¹ (Fe); 67 mg kg⁻¹ (Cu); 675 mg kg⁻¹ (Zn); 69 mg kg⁻¹ (Pb); and 1.93% (PO₄³⁻). The major crystalline constituent in the calculi of Sri Lanka is calcium oxalate monohydrate. Principal component analysis was used to identify the multi element relationships in kidney stones. Three components were extracted and the first component represents positively correlated Na-K-Mg-PO₄³⁻ whereas the␣second components represent the larger positively weighted Fe–Cu–Pb. Ca–Zn correlated positively in the third component in which Mn–Cu correlated negatively. This study indicates that during the crystallization of human urinary stones, Ca shows more affinity towards oxalates whereas other alkali and alkaline earths precipitate with phosphates.Contribution from the Environmental Geology Research Group (EGRG), Department of Geology, University of Peradeniya, Sri Lanka.     

Chlorophyll fluorescence measures of seagrasses <Emphasis Type="Italic">Halophila ovalis</Emphasis> and <Emphasis Type="Italic">Zostera capricorni</Emphasis> reveal differences in response to experimental shading

In coastal waters and estuaries, seagrass meadows are often subject to light deprivation over short time scales (days to weeks) in response to increased turbidity from anthropogenic disturbances. Seagrasses may exhibit negative physiological responses to light deprivation and suffer stress, or tolerate such stresses through photo-adaptation of physiological processes allowing more efficient use of low light. Pulse Amplitude Modulated (PAM) fluorometery has been used to rapidly assess changes in photosynthetic responses along in situ gradients in light. In this study, however, light is experimentally manipulated in the field to examine the photosynthesis of Halophila ovalis and Zostera capricorni. We aimed to evaluate the tolerance of these seagrasses to short-term light reductions. The seagrasses were subject to four light treatments, 0, 5, 60, and 90% shading, for a period of 14 days. In both species, as shading increased the photosynthetic variables significantly (P < 0.05) decreased by up to 40% for maximum electron transport rates (ETR_max) and 70% for saturating irradiances (E_k). Photosynthetic efficiencies (α) and effective quantum yields (ΔF/Fm′) increased significantly (P < 0.05), in both species, for 90% shaded plants compared with 0% shaded plants. H. ovalis was more sensitive to 90% shading than Z. capricorni, showing greater reductions in ETR_max, indicative of a reduced photosynthetic capacity. An increase in E_k, Fm′ and ΔF/Fm′ for H. ovalis and Z. capricorni under 90% shading suggested an increase in photochemical efficiency and a more efficient use of low-photon flux, consistent with photo-acclimation to shading. Similar responses were found along a depth gradient from 0 to10 m, where depth related changes in ETR_max and E_k in H. ovalis implied a strong difference of irradiance history between depths of 0 and 5–10 m. The results suggest that H. ovalis is more vulnerable to light deprivation than Z. capricorni and that H. ovalis, at depths of 5–10 m, would be more vulnerable to light deprivation than intertidal populations. Both species showed a strong degree of photo-adaptation to light manipulation that may enable them to tolerate and adapt to short-term reductions in light. These consistent responses to changes in light suggest that photosynthetic variables can be used to rapidly assess the status of seagrasses when subjected to sudden and prolonged periods of reduced light.     

Geochemistry of leachates from the El Fraile sulfide tailings piles in Taxco, Guerrero, southern Mexico

Leachates from the El Fraile tailings impoundment (Taxco, Mexico) were monitored every 2 months from October 2001 to August 2002 to assess the geochemical characteristics. These leachates are of interest because they are sometimes used as alternative sources of domestic water. Alternatively, they drain into the Cacalotenango creek and may represent a major source of metal contamination of surface water and sediments. Most El Fraile leachates show characteristics of Ca–SO₄, (Ca+Mg)–SO₄, Mg–SO₄ and Ca–(SO₄+HCO₃) water types and are near-neutral (pH=6.3–7.7). Some acid leachates are generated by the interaction of meteoric water with tailings during rainfall events (pH=2.4–2.5). These contain variable levels of SO₄ ²⁻ (280–29,500 mg l⁻¹) and As (<0.01–12.0 mg l⁻¹) as well as Fe (0.025–2352 mg l⁻¹), Mn (0.1–732 mg l⁻¹), Zn (<0.025–1465 mg l⁻¹) and Pb (<0.01–0.351 mg l⁻¹). Most samples show the highest metal enrichment during the dry seasons. Leachates used as domestic water typically exceed the Mexican Drinking Water Guidelines for sulfate, hardness, Fe, Mn, Pb and As, while acidic leachates exceed the Mexican Guidelines for Industrial Discharge Waters for pH, Cu, Cd and As. Speciation shows that in near-neutral solutions, metals exist mainly as free ions, sulfates and bicarbonates, while in acidic leachates they are present as sulfates and free ions. Arsenic appears as As^(V) in all samples. Thermodynamic and mineralogical evidence indicates that precipitation of Fe oxides and oxyhydroxides, clay minerals and jarosite as well as sorption by these minerals are the main processes controlling leachate chemistry. These processes occur mainly after neutralization by interaction with bedrock and equilibration with atmospheric oxygen.     

Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

The As-Contaminated Elqui River Basin: a Long Lasting Perspective (1975–1995) Covering the Initiation and Development of Au–Cu–As Mining in the High Andes of Northern Chile

The Elqui watershed (northern Chile) constitutes a highly contaminated river system, with arsenic exceeding by up to three orders of magnitude the average for river waters. There are three main reasons that explain this contamination: (1) the regional geology and hydrothermal (mineralizing) processes that developed in this realm during Miocene time; (2) the later unroofing–erosion–oxidation–leaching of As–Cu rich sulfide ores, a process that have been taking place for at least 10,000 years; and last but not least (3) mining activities at the high-altitude (>4000 m above sea level) Au–Cu–As El Indio mine, from the late 1970s onwards. The El Indio mineral deposit hosted large veins of massive sulfides, including the important presence of enargite (Cu₃AsS₄). The continuous natural erosion of these veins and their host rocks (also rich in As and Cu) during Holocene time, led to important and widespread metal dispersion along the river system. During the studied pre mining period (1975–1977), the high altitude river Toro waters already showed very large As concentrations (0.36–0.52 mg l⁻¹). The initiation of full scale mining at El Indio (1980 onwards) led to an increase of these values, reaching a concentration of 1.51 mg l⁻¹ As in 1995. During the same year other rivers of the watershed reached peak As concentrations of 0.33 (Turbio) and 0.11 mg l⁻¹ (Elqui). These figures largely exceed the USEPA regulations for drinking water (0.01 mg l⁻¹ As), and about 10% of the total As data from the river Elqui (and 70% from the river Turbio) are above the maximum level allowed by the Chilean law for irrigation water (0.1 mg l⁻¹ As).     

Distribution of nitrogen species in groundwater aquifers of an industrial area in alluvial Indo-Gangetic Plains—a case study

The groundwater samples collected from the shallow and deep groundwater aquifers of an industrial area of the Kanpur city (Uttar Pradesh, India) were analyzed for the concentration levels and distribution pattern of nitrogenous species, such as nitrate-nitrogen (NO₃-N), nitrite-nitrogen (NO₂-N), ammonical-nitrogen (NH₄-N), organic-nitrogen (Org-N) and total Kjeldahl-nitrogen (TKN) to identify the possible contamination source. Geo-statistical approach was adopted to determine the distribution and extent of the contaminant plume. In the groundwater aquifers NO₃-N, NO₂-N, NH₄-N, TKN, Org-N and Total-N ranged from 0.10 to 64.10, BDL (below detection limit)-6.57, BDL-39.00, 7.84–202.16, 1.39–198.97 and 8.89–219.43 mg l⁻¹, respectively. About 42% and 26% of the groundwater samples of the shallow and deep groundwater aquifers, respectively, exceeded the BIS (Bureau of Indian Standards) guideline value of 10 mg l⁻¹ for NO₃-N and may pose serious health hazards to the people of the area. The results of the study revealed that the groundwater aquifers of the study area are highly contaminated with the nitrate and indicates point source pollution of nitrate in the study area.     

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 induces reactive oxygen species,damages sperm,and impairs fertilisation in the sea urchin <Emphasis Type="Italic">Anthocidaris crassispina</Emphasis>

We demonstrated that environmentally relevant levels of UVA and UVB can reduce sperm motility (UVA: by 38–58%; UVB: by 42–85%; P < 0.05) and subsequently fertilisation success (UVA: by 38–72%; UVB: by 91–98%; P < 0.05) of urchins (Anthocidaris crassispina) in a dose-dependent manner, implicating that recruitment of urchin populations might be reduced by UVR (ultraviolet radiation) prevailing in their natural habitats. Concomitantly, reactive oxygen species (ROS) production was enhanced by UVA and UVB in a dose-dependent manner (UVA: by 1.3-fold; UVB: by 6.6–7.3-fold; P < 0.05), and the increase in ROS resulted in an increase in lipid peroxidation (LPO) in urchin sperm (UVA: by 4.2–7.2-fold; UVB: by 2.3–2.7-fold; P < 0.05). This study demonstrated that ROS production and oxidative damages enhanced by UVR may account for the observed declines in sperm motility and fertilisation, and suggests that levels of UVR prevailing in the environment may pose a significant threat to the reproductive success of natural populations of urchins spawning in shallow waters.     

Manipulation of food and photoperiod promotes out-of-season gametogenesis in the green sea urchin, Strongylocentrotus droebachiensis: implications for aquaculture

Green sea urchins, Strongylocentrotus droebachiensis OF Müller, collected off the coast of New Hampshire, USA, in late February 1995, were brought into the laboratory and fed an artificial diet ad libitum, and subjected to a photoperiod advanced by 4 months. During this study, temperatures and salinities for experimental urchins mirrored those recorded at the collection site. We examined the effects of changes in feeding regime and photoperiod on gametogenesis and compared the experimental urchins with those from the source population. During the 7-month period, experimental urchins showed no detectable changes in mean test height or diameter. Experimental urchins had a significantly higher gonad index (GI) in March, April and May (18 ± 6%) compared with field urchins in March (11 ± 3%). Subsequently, experimental urchins had a mean monthly GI of 25 to 30%, while the mean GI for field urchins was 11 to 13%. Gonial cell mitosis and gametogenesis occurred earlier in experimental male and female urchins compared with field urchins. Stereological and histological observations and stage–frequency data showed that the ovaries of experimental urchins were large because of the accelerated development of nutritive phagocytes, the volume fraction (V _v) of which was 89 to 90% of the gonad, while new vitellogenic primary oocytes occupied <1% V _v. In males, stereological and histological observations and stage–frequency data suggested a mobilization of materials from the nutritive phagocytes beginning between June and August, i.e. earlier than in females, and, by September, new gametes occupied a V _v of 49 ± 3% of the testes. Oocyte size–frequency distributions demonstrated that most primary oocytes were <80 μm in diameter between March and September, suggesting that cold temperatures may be needed for completion of vitellogenesis. We describe changes in the two principal cell types in the germinal epithelium of urchin gonads and indicate how knowledge of their population dynamics may be useful in aquaculture applications. Received: 21 February 1997 / Accepted: 3 June 1998     

S–O–C isotopic picture of sulphate–methane–carbonate system in freshwater lakes from Poland. A review

Microbial oxidation of organic compounds (including methane), in freshwater sediments, may result in precipitation of carbonates, which may become an important geochemical archive of paleoenvironmental variations. Most probably low δ¹³C value in calcite in eutrophic systems results from an advanced oxidation of organic compounds in turbulent or/and sulphate-rich conditions. Likewise, high δ¹³C value in calcite from organic-rich sediments may evidence low redox potential of the freshwater system. Oxidation of methane and organic matter results in significant isotope effects in sulphates dissolved in water. Therefore, to better understand the origin of carbon isotope signal in carbonates, concentration and stable isotope measurements in dissolved sulphate (water column), bubble methane and calcite (freshwater sediments) have been carried out in 24 lakes, 2 ponds and 4 rivers in Poland. The highest concentration of sulphate has been detected in rivers (85.47 SO₄ ²⁻ mg/l) and an artificial lake (70.30 SO₄ ²⁻ mg/l) located in the extremely SO₄ ²⁻-polluted region called the “Black Triangle”. The lowest concentration of sulphate is found in dystrophic and mountain lakes (from 0.5 SO₄ ²⁻ to about 3 mg/l). The lowest δ³⁴S(SO₄ ²⁻) and δ¹⁸O(SO₄ ²⁻) values occur in unpolluted lakes in eastern Poland (−0.94 and 1.38‰, respectively). The highest S and O isotopic ratios are found in a polluted lake in western Poland (δ¹⁴S(SO₄ ²)=12.95‰) and in a dystrophic lake in eastern Poland (δ¹⁸O(SO₄ ²) = 16.15‰) respectively. It is proposed that δ³⁴SO₄ ²⁻ and (¹⁸O(SO₄ ²⁻) values in lakes represent a good tool to assess and quantify anthropogenic impact by acid precipitation and to monitor variations in the trophic state and redox processes controlled by biodegradation of organic compounds in sediments and water column. In general, increasing depth (up to 12 m) of the water column is associated with decreasing trend the δ¹³C(CH₄) value from about –35 to about –78‰. However, δ¹³C value in sedimentary calcite (δ¹³C vary from –10 to 0.5‰) shows opposite trends as compared to the corresponding methane. This is probably due to redox processes and distribution of heavy isotopes between methane and calcite. Likewise, turbulent water (river) show high δ¹³C value in methane and low δ¹³C value in calcite—this is probably due to an enhanced oxidation of methane producing ¹³C-depleted CO₂. In contrast to clean lakes, it is observed that an increase of the δ¹³C(CH₄) value occurs with increasing depth of the water column in a strongly SO₄ ²⁻-contaminated lake. This is probably due to a loss of biological buffering potential of the lake accompanied by an active oxidation of methane precursors.     

Mineralogical and geochemical characterization of arsenic in an abandoned mine tailings of Korea

The mineralogical and chemical characteristics of As solid phases in arsenic-rich mine tailings from the Nakdong As–Bi mine in Korea was investigated. The tailings generated from the ore roasting process contained 4.36% of As whereas the concentration was up to 20.2% in some tailings from the cyanidation process for the Au extraction. Thin indurated layers and other secondary precipitates had formed at the surfaces of the tailings piles and the As contents of the hardened layers varied from 2.87 to 16.0%. Scorodite and iron arsenate (Fe₃AsO₇) were the primary As-bearing crystalline minerals. Others such as arsenolamprite, bernardite and titanium oxide arsenate were also found. The amorphous As–Fe phases often showed framboidal aggregates and gel type textures with desiccation cracks. Sequential extraction results also showed that 55.7–91.1% of the As in tailings were NH₄-oxalate extractable As, further confirmed the predominance of amorphous As–Fe solid phases. When the tailings were equilibrated with de-ionized water, the solution exhibited extremely acidic conditions (pH 2.01–3.10) and high concentrations of dissolved As (up to 29.5 mg L⁻¹), indicating high potentials for As to be released during rainfall events. The downstream water was affected by drainage from tailings and contained 12.7–522 μg L⁻¹ of As. The amorphous As–Fe phases in tailings have not entirely been stabilized through the long term natural weathering processes. To remediate the environmental harms they had caused, anthropogenic interventions to stabilize or immobilize As in the tailings pile should be explored.     

Effects of dissolved ammonium addition and host feeding with Artemia salina on photoacclimation of the hermatypic coral Stylophora pistillata

 Effects of nutrient treatments on photoacclimation of the hermatypic coral Stylophora pistillata (Esper) were studied. Studies on photoacclimation of colonies from different light regimes in the field were evaluated and used to design laboratory experiments. Coral colonies were collected in the Gulf of Eilat (Israel) from January to March 1993. Exterior branches of colonies from different depths (1 to 40 m) displayed different trends in production characteristics at reduced and very low levels of illumination. From 24 ± 3% to 12 ± 2% of incident surface photosynthetic active radiation (PAR_o), zooxanthella population density and chlorophyll a+c per 10⁶ zooxanthellae increased, a trend seen in the range of light levels optimal for coral growth (90 to 30% PAR_o). The P _max of CO₂ per 10⁶ zooxanthellae decreased, while P _max of CO₂ per 10³ polyps increased, indicating an increase in zooxanthella population density at low light levels. Proliferous zooxanthella frequency (PZF, a measure of zooxanthella division) declined significantly at light levels <18 ± 3% PAR_o. At the lowest levels of illumination (<5% PAR_o), zooxanthella population density decreased, as did the PZF; chl a+c per 10⁶ zooxanthellae was unchanged. In 28-d experiments, exterior coral branches from the upper surfaces of colonies from 3 m depth (65 ± 4% PAR_o) were incubated in aquaria under bright (80 to 90% PAR_o), reduced (20 to 30% PAR_o), and extremely low (2 to 4% PAR_o) light intensities. At each light intensity, the corals were maintained in three feeding treatments: sea water (SW); ammonium enriched SW (SW + N); SW with Artemia salina nauplii (SW + A). An increase in P _max of CO₂ per 10³ polyps was found in corals acclimated to reduced light (20 to 30% PAR_o) in nutrient-enriched SW, while in SW, where the increase in zooxanthella population density was smaller, it did not occur. Nutrient enrichments (SW + N at 2 to 4% PAR_o and SW + A at 20 to 30% PAR_o) increased zooxanthella population density, but had no effect on chl a+c per 10⁶ zooxanthellae. Acclimation for 14 d to reduced (10 to 20% PAR_o) and extremely low (1 to 3% PAR_o) light intensities shifted ¹⁴C photoassimilation into glycerol and other compounds (probably glycerides), rather than sugars. Both ammonium addition and feeding with Artemia salina nauplii resulted in an increase in photosynthetic assimilation of ¹⁴C into amino acids. We conclude that acclimation to reduced light consists of two processes: an increase in photosynthetic pigments and in zooxanthella population density. Both processes require nitrogen, the increase in zooxanthella population density needing more; this adaptation is therefore limited in nitrogen-poor sea water. Received: 19 June 1998 / Accepted: 13 June 2000     

Photosynthesis, respiration and calcification of a zooxanthellate scleractinian coral under submerged and exposed conditions

An experimental set-up was designed to investigate photosynthesis, respiration and calcification of zooxanthellate scleractinian corals under submerged and exposed conditions. The results of experiments to determine the effect of exposure to air on the metabolism of Stylophora pistillata (Esper, 1797) revealed that: (1) maximum gross photosynthesis ( p _{g max}) is 3.6 times higher in water than in air; (2) an indicator of photoadaptation (I _k ) does not reveal any difference between water and air; (3) the difference between submerged and aerial respiration is not statistically significant; (4) aerial photosynthesis–irradiance (P–I) curves display lower initial slopes (α) than aquatic P–I curves; (5) there is no calcification in air. Received: 7 February 1997 / Accepted: 4 March 1997     

Automated method for the determination of total arsenic and selenium in natural and drinking water by HG-AAS

A multicommutated flow system was designed and evaluated for the determination of total arsenic and selenium by Hydride Generation Atomic Absorption Spectrometry (HG-AAS). It was applied to the determination of arsenic and selenium in samples of natural and drinking water. Detection limits were 0.46 and 0.08 μg l⁻¹ for arsenic and selenium, respectively; sampling frequency was 120 samples h⁻¹ for arsenic and 160 samples h⁻¹ for selenium. Linear ranges found were 1.54–10 μg l⁻¹ (R = 0.999) for arsenic and 0.27–27 μg l⁻¹ (R = 0.999) for selenium. Accuracy was evaluated by spiking various water samples and using a reference material. Recoveries were in the range 95–116%. Analytical precision (s _r (%), n = 10) was 6% for both elements. Compared with the Standard Methods, APHA, 3114B manual method, the system consumes at least 10 times less sample per determination, and the quantities of acid and reducing agent used are significantly lower with a reduction in the generation of pollutants and waste. As an additional advantage, the system is very fast, efficient and environmentally friendly for monitoring total arsenic and selenium levels in waters.     

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.