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.     

Assessment of sulfurous springs in the west of Iraq for balneotherapy,drinking, irrigation and aquaculture purposes

This research deals with the sulfurous spring waters flow along the course of the Euphrates River in western Iraq in the area extended between Haqlaniya and Hit within the Al-Anbar governorate. Eleven springs (3 in Haqlanya, 4 in Kubaysa and 4 in Hit) have been addressed for the purpose of water evaluation for balneology, drinking, irrigation and aquaculture (fish farming). In order to meet the objectives of this research, all springs were sampled and analyzed for the total dissolved solid, electrical conductivity, pH, temperature, major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺), major anions (SO₄ ^2?, Cl^?, HCO₃ ^? and CO₃ ^2?), minor anions (PO₄ ^3?and NO₃ ^?) as well as the trace elements that included Pb, Zn, Cd, Ni, Fe, Mn, Cu, Br, F, Ba, B, Sr, Al, As, Cr, Hg and Se. The International Standards of World Health Organization are used for assessing the water quality. The results revealed that the springs belong to the tepid springs of 27–30 °C and classified as hypothermal to the thermal springs. Lithochemistry and geochemical processes clearly affected the water chemistry. The hydrogeochemical processes are responsible for the element enrichment in water by the chemical dissolution of carbonate and gypsum and evaporation as well. The results of the study indicate the possibility of using spring water for therapeutic purposes, but not allowed for drinking and aquaculture (fish farming), except those free of H₂S gas. On the other hand, it can be used for irrigation with risk. However, soil type as well as proper selection of plants should be taken into consideration.     

Suitability for human consumption and agriculture purposes of Sminja aquifer groundwater in Zaghouan (north-east of Tunisia) using GIS and geochemistry techniques

In Tunisia, the water resources are limited, partially renewable and unequally distributed between the wet north and the dry south of the country. The Sminja aquifer in Zaghouan city is located in north-east of Tunisia, between latitudes 36°38′ and 36°47′ and longitudes 9°95′ and 10°12′. This aquifer is used to satisfy the population needs for their domestic purposes and agricultural activities. Water analyses results are expressed by many methods, among which are geochemical methods combined with the geographic information system (GIS) (all schematic presentations of the diagram software (Piper, Riverside, Wilcox…), which can be used to assess the suitability of the Sminja aquifer groundwater for human consumption and irrigation purposes. A total of 23 wells were sampled in January 2013, and the concentrations of major cations (Na⁺, Ca²⁺, Mg²⁺ and K⁺), major anions (Cl^?, SO₄ ^2? and HCO₃ ^?), electrical conductivity and total dissolved solids were analysed. In the Sminja groundwater, the order of the cations dominance was Na > Ca > Mg > K and that of the anions was Cl > HCO₃ > SO₄. All of the analysed samples of the study area exceed chemical values recommended by the World Health Organisation guidelines and Tunisian Standards (NT.09.14) for potability but with different percentages. The aquifer spatial distribution of saturation indices reveals that all groundwater samples are under-saturated with gypsum, halite and anhydrite and are over-saturated with respect to calcite and dolomite based on water quality evaluation parameters for irrigation purposes; here, 87 % of samples in Sminja aquifer groundwater are suitable, whereas 13 % are unsuitable for irrigation uses.     

Evaluation of porous cup soil‐water samplers under laboratory conditions: Comparison of ceramic and PTFE cups

Three different types of soil solution samplers (two ceramic cups and PTFE) were tested in the laboratory to validate their use for collecting soil‐water samples and for monitoring the chemical composition of soil solutions. Interactions between porous materials and chemical solutions were examined under different experimental conditions for several major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺) and anions (HCO^‐ ₃, NO^‐ ₃, SO₄ ^2‐ and Cl^‐) and for several minor ions (NH⁺ ₄, NO^‐ ₄, PO₄ ^3‐and B).

The results show that ceramic cups are not inert for bicarbonate, calcium and phosphate ions. Their use is only valid for a limited number of ions such as chloride and nitrate which, however, are the most studied ions in field experiments. PTFE cups have less restrictions although their use in measuring sulphates, phosphates and ammonium presents some problems.

Choosing the appropriate type of cup depends on the objectives. In any case, laboratory experiments must be performed before installation.     

Geoenvironmental factors related to high incidence of human urinary calculi (kidney stones) in Central Highlands of Sri Lanka

An area with extremely high incidence of urinary calculi was investigated in the view of identifying the relationship between the disease prevalence and the drinking water geochemistry. The prevalence of the kidney stone disease in the selected Padiyapelella–Hanguranketa area in Central Highlands of Sri Lanka is significantly higher compared with neighboring regions. Drinking water samples were collected from water sources that used by clinically identified kidney stone patients and healthy people. A total of 83 samples were collected and analyzed for major anions and cations. The anions in the area varied in the order HCO₃ ^? > Cl^? > SO₄ ^2? > NO₃ ^? and cations varied in the order Ca²⁺ > Mg²⁺ > Na⁺ > K⁺ > Fe²⁺. The dissolved silica that occurs as silicic acid (H₄SiO₄) in natural waters varied from 8.8 to 84 mg/L in prevalence samples, while it was between 9.7 and 65 mg/L for samples from non-prevalence locations. Hydrogeochemical data obtained from the two groups were compared using the Wilcoxon rank-sum test. It showed that pH, total hardness, Na⁺, Ca²⁺ and Fe²⁺ had significant difference (p < 0.005) between water sources used by patients and non-patients. Elemental ratio plots, Gibbs’ plot and factor analysis indicated that the chemical composition of water sources in this area is strongly influenced by rock–water interactions, particularly the weathering of carbonate and silicate minerals. This study reveals a kind of association between stone formation and drinking water geochemistry as evident by the high hardness/calcium contents in spring water used by patients.     

Removal of Eu3+, Ce3+, Sr2+, and Cs+ ions from radioactive waste solutions by modified activated carbon prepared from coconut shells

As a biomass agricultural waste material, coconut shells were used for the preparation of high-quality modified activated carbon. Chemical modification of the surface of the prepared activated carbon is done by oxidation using H₂O₂ and HNO₃, respectively. The surface area and pore volume of the coconut shells activated carbon are increased by the chemical modification, and followingly the removal of the metals is improved. The structural morphology and composition of the modified activated carbon coconut shells (MACCS) were evaluated by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis–differential thermal analysis (TGA-DTA), scanning electron microscope (SEM), X-ray diffraction (XRD), surface area analysis (SAA), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis. The prepared MACCS has reasonably good chemical stability. The influence of solution pH, contact time, adsorbent dosage, adsorption temperature, initial metal concentrations, and interfering ions on the adsorption performance of the investigated ions onto the prepared sorbent was examined by a batch method. The selectivity sequence for sorption of Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions on MACCS was found to be Eu^3+?>?Ce^3+?>?Sr^2+?>?Cs⁺. The saturation capacities of MACCS for the studied metal ions were found to be 136.84, 85.55, 69.85, and 60.00?mg?g^?1 for Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions, respectively. The thermodynamic parameters, ΔH°, ΔS°, and ΔG° were also evaluated.     

Acid-base responses to lethal aquatic hypercapnia in three marine fishes

Ocean sequestration of CO₂ is proposed as a possible measure to mitigate environmental changes due to the increasing atmospheric concentration of the gas. However, toxic effects of CO₂ on marine organisms are poorly understood. We therefore studied acid–base responses and mortality during exposure to fatal levels of CO₂ in three marine fishes (Japanese flounder, Paralichthys olivaceus; yellowtail, Seriola quinqueradiata; and starspotted dogfish, Mustelus manazo). The teleosts died during exposure to seawater equilibrated with a gas mixture containing 5% CO₂ (water PCO₂ 4.95 kPa); 100% mortality occurred within 8 h for yellowtail and within 48 h for flounder. Only 20% mortality was recorded at 72 h for the dogfish during exposure to 7% CO₂ (water PCO₂ 6.96 kPa). Arterial pH (pH_a) initially decreased, but completely recovered within 1–24 h for the teleosts at 1% and 3%, although the recovery was slower and complete only at 1% (water PCO₂ 0.99 kPa) for the dogfish. During exposure to 5%, the flounder died after the pH_a had been completely restored, suggesting that the mortality was not due to plasma acidosis. During exposure to 1% hypercapnia, plasma [Cl^–] appeared to be the main counter ion to balance increases in plasma [HCO₃^-]. There was a 1:1 stoichiometry for the rise in [HCO₃^-] and the fall in [Cl^–] for the teleosts, whereas the ratio was 1:0.4 for the dogfish at 1% CO₂. At the higher levels of hypercapnia, the rise in [HCO₃^-] consistently exceeded the fall in [Cl^–], and plasma [Na⁺] significantly increased.These results do not agree with the generally accepted model for acid–base regulation in marine fish in which Na⁺/H⁺ exchangers are assumed to play a predominant role, and indicate that an acid–base regulatory mechanism differs between teleost and elasmobranch fishes, as well as the intensity of acidic stress.Communicated by T. Ikeda, Hakodate     

Removal of acid yellow 36 using Box–Behnken designed photoelectro-Fenton: a study on removal mechanisms

Photoelectro-Fenton was applied for the removal of acid yellow 36 (AY36) from synthetic aqueous solution using iron electrodes. A Box–Behnken design was used for optimization of the effects of pH, H₂O₂ concentration, current density, and reaction time. Individual effects of these variables were more important than their interaction effects. The derived model was in good agreement with the experimental results. Total organic carbon was determined in solution and sludge in order to clarify the removal mechanism. Increase of H₂O₂ concentration and current density led to domination of oxidation and coagulation mechanisms, respectively. The effects of scavenging and inhibiting agents were also investigated: (1) presence of alcohols can reduce the efficiency through competition with dye for reaction with hydroxyl radicals; (2) anions (NO₃^?, HCO₃^?, and H₂PO₄^?) scavenged hydroxyl radicals and reduced decolorization of AY36.     

A Critical Appraisal of Field Evidence From A Regional Survey for Acid Deposition Effects On Scottish Moorland Podzols

Samples have been collected from major horizons of 34 podzol profiles distributed throughout Scotland, all developed from granite or granitic tills and under Calluna moorland. the pH in water and calcium chloride pastes, exchangeable cations and cation exchange capacity, and extractable aluminium of the soils collected have been measured, and the results studied in relation to reported atmospheric deposition of H⁺, non-marine sulphur and nitrate. for all horizons, significant positive correlations were found between soil pH and rainfall mean pH, as might be expected when the critical load of H⁺ deposition is exceeded. Acidifying pollutant deposition also apparently increased soil extractable aluminium concentrations in the B and C horizons. However, exchangeable base cation concentrations tended to increase, rather than decrease, with increasing precipitation acidity. This effect was attributed to increases in biogeochemical cycling of base cations, increases in leaching inputs of base cations from overlying A/E horizon soils, and increases in the inputs of base cations leached from upslope. the results suggest that the simple steady state mass approach to the quantification of critical loads, as often applied, may be an oversimplification.     

Ackee apple (Blighia sapida) seeds: a novel adsorbent for the removal of Congo Red dye from aqueous solutions

The ability of ackee apple (AA) seeds to remove Congo Red (CR) dye from aqueous solution was investigated. AA was characterised using thermo gravimetric analyser, scanning electron microscopy, Braunauer Emmett Teller, pH_pzc, elemental analysis and Boehm titration. The effects of operational parameters such as adsorbent dosage, contact time, initial dye concentration and solution pH were studied in a batch system. pH has a profound influence on the adsorption process. Maximum dye adsorption was observed at pH 3.0. The reaction was fast, reaching equilibrium in 90 min. Adsorption data were best described by Langmuir isotherm and the pseudo-second-order kinetic model with a maximum monolayer coverage of 161.89 mg·g^?1. Both boundary layer and intraparticle diffusion mechanisms were found to govern the adsorption process. Thermodynamic parameters such as standard free energy change (Δ G ⁰), standard enthalpy change (Δ H ⁰), and standard entropy change (Δ S ⁰) were studied. Values of Δ G ⁰ varied between?30.94 and?36.56 kJ·mol^?1, Δ H ⁰ was 25.61 kJ·mol^?1, and Δ S ⁰ was 74.84 kJ·mol^?1·K^?1, indicating that the removal of CR from aqueous solution by AA was spontaneous and endothermic in nature. Regeneration and reusability studies were carried out using different eluents. AA gave the highest adsorption efficiency up to four cycles when treated with 0.3 M HCl. AA was found to be an effective adsorbent for the removal of CR dye from aqueous solution.     

Adsorptive features of banana (Musa paradisiaca) stalk-based activated carbon for malachite green dye removal

Chemically prepared activated carbon derived from banana stalk (BSAC) was used as an adsorbent to remove malachite green (MG) dye from aqueous solution. BSAC was characterised using thermogravimetric analyser, Brunauer Emmett Teller, Fourier transform infrared spectrometry, scanning electron microscopy, pH_pzc, elemental analysis and Boehm titration. The effectiveness of BSAC in adsorbing MG dye was studied as a function of pH, contact time, temperature, initial dye concentration and repeated desorption–adsorption processes. pH_pzc of BSAC was 4.5 and maximum dye adsorption occurred at pH 8.0. The rate of dye adsorption by BSAC was very fast initially, attaining equilibrium within 120 min following a pseudo-second-order kinetic model. Experimental data were analysed by Langmuir, Freundlich and Dubinin–Raduschevich isotherms. Equilibrium data fitted best into the Langmuir model, with a maximum adsorption capacity of 141.76 mg·g^?1. Δ G ⁰ values were negative, indicating that the process of MG dye adsorption onto BSAC was spontaneous. The positive values of Δ H ⁰ and Δ S ⁰ suggests that the process of dye adsorption was endothermic. The regeneration efficiency of spent BSAC was studied using 0.5 M HCl, and was found to be in the range of 90.22–95.16% after four cycles. This adsorbent was found to be both effective and viable for the removal of MG dye from aqueous solution.     

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.     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^?1) on ¹³⁷Cs adsorption–desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26–99.97%) of added ¹³⁷Cs (3.7?×?10³?7.03?×?10⁵ Bq l^?1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K _ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄ ⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K _ads and soil pH was observed. The ¹³⁷Cs adsorption–desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09–0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Hydrogeochemistry study and groundwater quality assessment in the north of Isfahan,Iran

This study presents the groundwater quality assessment in the north of Isfahan, Iran. In the study area, assessment and measurement of groundwater hydrochemical parameters such as pH, total dissolved solids (TDS), electrical conductivity (EC), sodium absorption ratio (SAR), total hardness, major cations (K⁺, Na⁺, Ca²⁺ and Mg²⁺) and major anions (Cl^?, \({\text{HCO}}_{ 3}^{ - } ,{\text{CO}}_{3}^{2 - }\) and \({\text{SO}}_{4}^{2 - }\)) concentrations were performed. Accordingly, the 66 water samples from different locations were collected during April and May 2015. Water samples collected in the field were analyzed in the laboratory for cations and anions using the standard methods. In this research, the analytical results of physiochemical parameters of groundwater were compared with the standard guideline values as recommended by the world health organization (WHO) for drinking and public health purposes. The pH values of groundwater samples varied from 7.05 to 8.95 with a mean of 7.78, indicating a neutral to slightly alkaline water. TDS values showed that 14% of the samples exceeds the desirable limit given by WHO. EC values varied from 213 to 4320 µS/cm, while 23% of the samples were more than the standard limit. Gibbs diagram had shown that 90% of the samples in the study area fall in the rock weathering zone, and this means that chemical weathering of rock-forming minerals is the main factor controlling the water chemistry in the study area. Irrigation suitability and risk assessment of groundwater are evaluated by measuring EC, %Na, SAR and RSC. According to the dominant cations and anions, five types of water were identified in the water samples: Ca-HCO₃, Ca-SO₄, Na-Cl, Na-HCO₃ and Na-SO₄. The results show that the majority of samples (30 samples, 45%) belongs to the mixed Na-SO₄ water type. Correlation analysis and principal component analysis was used to identify the relationship between ions and physicochemical parameters. Results indicated that 18 stations of the study area had the best quality and can be used for irrigation and drinking purposes in the future.     

Speciation of mercury in South African coals

Total mercury (Hg_TOT) concentrations were determined by inductively coupled plasma mass spectrometry (ICP MS) for South African Highveld coals. The distribution of Hg in coals was investigated using a four-stage sequential leaching protocol and isotope dilution/gas chromatography coupled to ICP MS (ID-GC-ICP MS). The results show that Hg_TOT ranged from 144 to 303?µg?kg^?1 with a mean of 199?±?26?µg?kg^?1, while Hg_TOT leached from coals using different solvents ranged between 103 and 310?µg?kg^?1 (mean: 218?±?60?µg?kg^?1). Hg leaching rates of 53–78% were achieved in crushed coals. Hg⁰, Hg²⁺, and CH₃Hg⁺ were identified in all coals. CH₃Hg⁺ in studied coals ranged between 0.1 and 0.4 (mean: 0.2) µg?kg^?1. GC ICP MS chromatograms also showed unknown Hg peaks which were identified as other organomercury species such as ethylmercury. Modes of occurrence of Hg in coals were variable with the organic-bound (37–40%) and the sulfide-bound (37–39%) being the dominant mercury forms. Increasing the HCl concentration in the used protocol increased the amount of Hg leached (16%) during this step.     

Adsorption of fluoride on clay minerals and their mechanisms using X-ray photoelectron spectroscopy

This research investigates the adsorption mechanisms of fluoride (F) on four clay minerals (kaolinite, montmorillonite, chlorite, and illite) under different F^? concentrations and reaction times by probing their fluoride superficial layer binding energies and element compositions using X-ray photoelectron spectroscopy (XPS). At high F^? concentrations (C ₀ = 5?C1000 mg·L^?1), the amount of F^? adsorbed (Q _F), amount of hydroxide released by clay minerals, solution F^? concentration, and the pH increase with increasing C ₀. The increases are remarkable at C ₀>50 mg·L^?1. The QF increases significantly by continuously modifying the pH level. At C ₀<5?C100 mg·L^?1, clay minerals adsorb H⁺ to protonate aluminum-bound surface-active hydroxyl sites in the superficial layers and induce F^? binding. As the C ₀ increases, F^?, along with other cations, is adsorbed to form a quasi-cryolite structure. At C ₀>100 mg·L^?1, new minerals precipitate and the product depends on the critical Al³⁺ concentration. At [Al³⁺]>10^?11.94 mol·L^?1, cryolite forms, while at [Al³⁺]<10^?11.94 mol·L^?1, AlF₃ is formed. At low C ₀ (0.3?C1.5 mg·L^?1), proton transfer occurs, and the F^? adsorption capabilities of the clay minerals increase with time.     

Removal of arsenic from aqueous solution by two types of nano TiO2 crystals

Titanium dioxide (TiO₂) is a promising sorbent for As removal. There are two main and physico-chemically distinct polymorphs of TiO₂ in nature, namely anatase and rutile. Since the difference of arsenic removal by the two polymorphs of TiO₂ is now well known, study on the arsenic removal efficiency and the underlying mechanism is of great significance in developing new remediation strategies for As-polluted waters. Here batch experiments were carried out in combination with instrumental analysis of X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) to investigate the effects, influential factors and mechanisms of As removal from aqueous solution by two types of nano TiO₂ crystals. The adsorption behavior of anatase and rutile for As(V) and As(III) are well described by Freundlich equations. Anatase had higher As removal efficiency and adsorption capacity than rutile. Solution pH had no influence on the As adsorption of anatase TiO₂, whereas the As removal by rutile TiO₂ was increased by 7?C18% with pH from 4 to 10. Presence of accompanying anions such as phosphate, silicate, nitrate and sulfate, decreased the As(V) and As(III) removal by both crystals, with phosphate being the most effective. However, removal of As by rutile TiO₂ was greatly enhanced in the presence of divalent cations i.e. Ca²⁺ and Mg²⁺. Shading of light decreased the removal of As(V) and As(III) of anatase by 15.5% and 17.5%, respectively, while a slight increase of As removal was observed in the case of Rutile TiO₂. FT-IR characterization of As(V) or As(III)-treated nano TiO₂ crystals indicated that both Ti-O and As-O groups participated in As adsorption. Both FT-IR and XPS analysis demonstrated that As(III) was photooxidated into As(V) when adsorbed by anatase under the light condition. Thus, the effect of crystal types and light condition on As removal should be taken into consideration when nano TiO₂ is applied for As removal from water.     

Buffer sensitivity of photosynthetic carbon utilisation in eight tropical seagrasses

Some of the mechanisms involved in inorganic carbon (Ci) acquisition by tropical seagrasses from the western Indian Ocean were described by Björk et al. (Mar Biol 129:363–366, 1997). However, since then, it has been found that an additional, buffer-sensitive, system of Ci utilisation may operate in some temperate seagrasses (Hellblom et al. in Aquat Bot 69:55–62, 2001, Hellblom and Axelsson in Photos Res 77:173–191, 2003); this buffer sensitivity indicates a mechanism in which electrogenic H⁺ extrusion may form acidic diffusion boundary layers, in which either HCO ₃ ^? –H⁺ is co-transported into the cells, or where HCO ₃ ^? is converted to CO₂ (as catalysed by carbonic anhydrase) prior to uptake of the latter Ci form. Because a buffer was used in the 1997 study, we found it important to reinvestigate those same eight species, taking into account the direct effect of buffers on this potential mode of Ci acquisition in these plants. In doing so, it was found that all seagrass species investigated except Cymodocea serrulata were sensitive to 50 mM TRIS buffer of the same pH as the natural seawater in which they grew (pH 8.0). Especially sensitive were Halophila ovalis, Halodule wrightii and Cymodocea rotundata, which grow high up in the intertidal zone (only ca. 50–65% of the net photosynthetic activity remained after the buffer additions), followed by the submerged Enhalus acoroides and Syringodium isoetifolium (ca. 75% activity remaining), while Thalassia hemprichii and Thalassodendron ciliatum, which grow in-between the two zones, were less sensitive to buffer additions (ca. 80–85% activity remaining). In addition to buffer sensitivity, all species were also sensitive to acetazolamide (AZ, an inhibitor of extracellular carbonic anhydrase activity) such that ca. 45–80% (but 90% for H. ovalis) of the net photosynthetic activity remained after adding this inhibitor. Raising the pH to 8.8 (in the presence of AZ) drastically reduced net photosynthetic rates (0–14% remaining in all species); it is assumed that this reduction in rates was due to the decreased CO₂ concentration at the higher pH. These results indicate that part of the 1997 results for the same species were due to a buffer effect on net photosynthesis. Based on the present results, it is concluded that (1) photosynthetic Ci acquisition in six of the eight investigated species is based on carbonic anhydrase catalysed HCO ₃ ^? to CO₂ conversions within an acidified diffusion boundary layer, (2) C. serrulata appears to support its photosynthesis by extracellular carbonic anhydrase catalysed CO₂ formation from HCO ₃ ^? without the need for acidic zones, (3) H. ovalis features a system in which H⁺ extrusion may be followed by HCO ₃ ^? –H⁺ co-transport into the cells, and (4) direct, non-H⁺-mediated, uptake of HCO ₃ ^? is improbable for any of the species.     

细颗粒物(PM_(2.5))主要组分模拟溶液对发光细菌的光抑制分析

为明确NH_4~+、 NO_3~-、SO_4~(2-)及金属等组分在水溶性提取液对发光细菌的光抑制过程中所起的作用,参照PM_(2.5)样品提取液浓度,模拟配制与3级以上PM_(2.5)样品提取液中主要组分:硫酸盐、硝酸盐、氨盐相同浓度的溶液,同时选取与PM_(2.5)可溶性提取液发光抑制率相关性较强的铅、锌,配制不同浓度级别模拟溶液,测试各单一组分对发光细菌的发光抑制率及其混合溶液对发光细菌的联合影响效应。基于毒性单位法(TU)、相加指数法(AI)和混合毒性指数法(MTI)评价了混合体系联合影响的作用类型。结果表明,与3~6级PM_(2.5)可溶性提取液中硫酸氨、硫酸氢氨、硝酸氨、硫酸锌和硝酸铅浓度相同的模拟溶液对发光细菌的发光没有抑制作用。不同的评价方法对PM_(2.5)主要组分混合体系联合效应评价结果具有较好的一致性,硫酸氨、硝酸氨、硫酸氢氨混合溶液中,对发光细菌的光抑制均为硫酸氢氨的独立作用,硫酸锌与硝酸铅的混合体系,锌和铅对发光细菌的联合影响效应表现为协同,硫酸氨、硝酸氨、硫酸氢氨与硫酸锌、硝酸铅的多元混合体系呈现协同作用。     

Photosynthetic carbon acquisition in the red alga Gracilaria conferta

In this continuing study on photosynthesis of the marine red alga Gracilaria conferta, it was found that ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) in crude extracts had a K _m (CO₂) of 85 M. Since seawater contains only ca. 10 M CO₂, it appears that this alga must possess a CO₂ concetrating system in order to supply sufficient CO₂ to the vicinity of the enzyme. Because this species is a C₃ plant (and thus lacks the C₄ system for concentrating CO₂), but can utilize HCO₃ ^- as an exogenous carbon source, we examined whether HCO₃ ^- uptake could be the initial step of such a CO₂ concetrating system. The surface pH of G. conferta thalli was 9.4 during photosynthesis. At this pH, estimated maximal uncatalyzed HCO₃ ^- dehydration (CO₂ formation) within the unstirred layer was too slow to account for measured phostosynthetic rates, even in the presence of an external carbonic anhydrase inhibitor. This observation, and the marked pH increase in the unstirred layer following the onset of light, suggests that a HCO₃ ^- transport system (probably coupled to transmembrane H⁺/OH^- fluxes) operates at the plasmalemma level. The involvement of surface-bound carbonic anhydrase in such a system remains, however, obscure. The apparent need of marine macroalgae such as G. conferta for CO₂ concentrating mechanisms is discussed with regard to their low affinity of Rubisco to CO₂ and the low rate of CO₂ supply in water. The close similarity between rates of Rubisco carboxylation and measured photosynthesis further suggests that the carboxylase activity, rather than inorganic carbon transport and intercoversion events, could be an internal limiting factor for photosynthetic rates of G. conferta.