The impact of inorganic tin on the planktonic cyanobacterium Synechocystis aquatilis: the effect of pH and humic acid

The influence of inorganic tin compounds on the unicellular cyanobacterium Synechocystis aquatilis was studied, and its dependence on changing pH of the surrounding medium and the presence of humic acid. Both Sn(II) and Sn(IV), used as chlorides (at the concentrations 1-10 mg litre(-1)), inhibit the growth and chlorophyll a content of the cyanobacterium cultures, but only under alkaline conditions. Generally, the observed tin toxicity increased with increase of metal concentration, time of exposure and pH value of the medium (in the range 7-9.8). Sn(II) seems to be more toxic than Sn(IV). At the lowest studied metal concentration (1 mg litre(-1)), Sn(II) caused a 36 and 40% decrease in growth and chl a content, respectively, after 96 h exposure at pH 9.8, while Sn(IV) caused even a slight increase of both physiological parameters (hormetic effect). Similar increases in growth and chl a content were also observed at a high Sn (II) and Sn(IV) concentration (10 mg litre(-1)), but only in cultures exposed to metal at pH 7. At high pH (9.8), 10 mg litre(-1) of Sn(II) and Sn(IV) significantly suppressed both the growth of the cyanobacterium (by 54.2 and 26.1%, respectively) and the chl a content in cultures (by 58.2 and 24%, respectively). Humic acid reduced the toxicity of tin towards the cyanobacterium. The observed effects of pH and complexing ligand on the inorganic tin toxicity are discussed in the context of changing, chemical metal speciation and bioavailability.     

Cadmium availability to wheat grain in soils treated with sewage sludge or metal salts

Grain Cd concentrations were determined in wheat (Triticum aestivum L.) grown in 1999, 2001 and 2003, at six sludge cake field experiments. Three of these sites also had comparisons with Cd availability from metal amended liquid sludge and metal salts. Grain Cd concentrations in all years and at all sites were significantly linearly correlated with NH4NO3 extractable Cd and soil total Cd (P<0.001). Soil extractability was greater in the liquid sludge and metal salt experiments than in the cake experiments, as were grain Cd concentrations. Across all the sites, NH4NO3 extractable soil Cd was no better at predicting grain Cd than soil total Cd. Stepwise multiple linear regression analysis showed that soil total Cd, pH and organic carbon were the only significant (P<0.001) variables influencing wheat grain Cd concentrations, explaining 78% of the variance across all field experiments (1408 plots). This regression predicted that the current UK soil total Cd limit of 3 mg kg(-1) was not sufficiently protective against producing grain above the European Union (EU) grain Cd Maximum Permissible Concentration (MPC) of 0.235 mg Cd kg(-1) dry weight, unless the soil pH was > 6.8. Our predictions show that grain would be below the MPC with > 95% confidence with the proposed new EU draft regulations permitting maximum total Cd concentrations in soils receiving sludge of 0.5 mg kg(-1) for soils of pH 5-6, 1 mg kg(-1) for soils of pH 6-7, and 1.5 mg kg(-1) for soils of pH > or = 7.     

Cadmium availability to wheat in five soil series from the Yonne district, Burgundy, France

Preliminary results from the French ASPITET programme demonstrated that Cd background levels in agricultural soils can vary greatly (0.02-6.9 mg Cd kg(-1)) depending on parent material and pedogenic processes (Baize, 1997). However, the total Cd content in soil is often not significantly related to the Cd concentration in edible plant parts. A field case study was undertaken across the southern part of the Yonne district, Burgundy, France. This area has various soil series with either low or high geochemical Cd content in the topsoil. Cd availability in soils sampled at 16 sites belonging to five soil series was investigated using single extractions. In addition, shoots (at stem elongation) and grains (at harvest) of field-grown wheat were collected at the same sites and analysed for macronutrients and trace elements. Cd concentrations in grain varied from 0.015 to 0.146 mg Cd kg(-1) DM depending on soil characteristics, soil series, and plant mineral composition. Cd grain concentrations did not reflect total Cd content in the surface soil layer; however, they were correlated with Cd extracted by a 0.1 M calcium nitrate unbuffered solution, and to a lesser extent with either soil pH or CEC. These three parameters may be useful guides to predict Cd in wheat grain harvested in the Yonne district. An inverse relationship was found between Cd and Cu contents in grain. The highest Cd concentrations in wheat grain occurred in plants grown on Aubues soils which had marginal Cu and Zn deficiencies in shoots. In order of Cd accumulation in wheat grain, soil series may be ranked as follows: Domérien < Carixien, Terres Noires < Sols Marron < Aubues.     

Value of biochars from Miscanthus x giganteus cultivated on contaminated soils to decrease the availability of metals in multicontaminated aqueous solutions

The objective of this study was to evaluate the sorption efficiency of eight biochars, made from Miscanthus x giganteus cultivated on contaminated agricultural soil, in aqueous solutions contaminated with metals alone or mixed with polycyclic aromatic hydrocarbons. These biochars were produced in different pyrolysis conditions (temperature, 400/600 °C; heating rate, 5/10 °C min⁻¹; duration, 45/90 min) and compared with an uncontaminated commercialized biochar made of wood. The physicochemical characterization of the Miscanthus biochars confirmed the impact of the pyrolysis on the biochar parameters with substantial differences between the biochars in terms of pH, cation exchange capacity, and specific surface area. The sorption experiment showed higher sorption efficiency of Cd, Pb, and Zn for the Miscanthus biochars produced at 600 °C compared with the biochars produced at 400 °C when the aqueous solutions were mono- or multicontaminated. Furthermore, the desorption study showed that the sorption process was largely irreversible. Therefore, the high sorption capacity of Miscanthus biochars and the low sorption reversibility confirmed that these biochars are a suitable sorbent for metals.

     

Modeling heterogeneous ClNO2 formation,chloride availability,and chlorine cycling in Southeast Texas

Nitryl Chloride (ClNO₂) mixing ratios above 1 ppbv have been measured off the coast of Southeast Texas. ClNO₂ formation, the result of heterogeneous N₂O₅ uptake on chloride-containing aerosols, has a significant impact on oxidant formation for the Houston area. This work reports on the modeling of ClNO₂ formation and describes the sensitivity of ClNO₂ formation to key parameters. Model sensitivity analyses found that: (1) Chloride availability limits the formation of nitryl chloride at ground level but not aloft; (2) When excess particulate chloride was assumed to be present at ground level through sea salt, ClNO₂ concentrations increased in some locations by a factor of 13, as compared to cases where sea salt chloride was assumed to be limited; (3) Inland formation of ClNO₂ seems feasible based on chloride availability and could have a large impact on total ClNO₂ formed in the region; and (4) ClNO₂ formation is quite sensitive to the assumed yield of ClNO₂ from N₂O₅ uptake. These results demonstrate that there is a need for further field studies to better understand the geographic extent of ClNO₂ formation and the atmospheric conditions which control partitioning of chloride into the particle phase. In addition, this work examined the role of ClNO₂ in the cycling of chlorine between chloride and reactive chlorine radicals. The modeling indicated that the majority of reactive chlorine in Texas along the Gulf coast is cycled through ClNO₂, demonstrating the importance of including ClNO₂ into photochemical models for this region.     

Cadmium in soil solutions from a transect of soils away from a fertiliser bin

The effects of high inputs of phosphate fertiliser on Cd concentrations were studied in soil solutions extracted from topsoils. Soils were sampled along a transect at distances of 1-100 m away from a fertiliser bin. The transect was sampled four times during 1 year. Soil solutions were analysed for Cd, pH, major cations and anions, and other heavy metals (As, Cr, Cu, Pb). For one of the transect samplings, soil total Cd, Cr, Cu, Pb and P were also measured. Cd speciation in the soil solutions was calculated by the GEO-CHEM-PC computer program. Chemical composition varied substantially along the transect, and also between samplings, indicative of seasonal effects and the influence of a fresh application of superphosphate fertiliser during the year. Application of fertiliser decreased soil solution pH and increased the levels of heavy metals in soil solution. Generally, soil total Cd, Cr, Cu, Pb, and P decreased with increasing distance from the fertiliser bin. Correlations between P and the four heavy metals were: P and Cd (R2 = 0.978), P and Cr (R2 = 0.712), P and Pb (R2 = 0.538), P and Cu (R2 = 0.267). Less than 1% of the total Cd in the soil samples was found in the soil solution. The free metal ion Cd2+ accounted for 55-90% of solution Cd. Of the complexed species of Cd, the chloride and sulphate complexes were usually the most important, even when nitrate and phosphate concentrations were relatively high. The presence of As, Cr, Cu and Pb had no effect on Cd speciation.     

Antioxidant and metabolism responses to polyphenol stress in cyanobacterium Microcystis aeruginosa

Three common polyphenol compounds Gallic Acid (GA), Pyrogallic Acid (PA) and Catechol (CA) are known to have allelochemical-exhibiting inhibitory effects on the growth of the cyanobacterium Microcystis aeruginosa (M. aeruginosa). Metabolism and antioxidant responses in M. aeruginosa were investigated to elucidate the mechanism by which the three polyphenols inhibit algal growth. The inhibition effects of polyphenols were in the order of CA > PA > GA. The GA and CA exposures increased protein contents, superoxide dismutase (SOD) activity, catalase (CAT) activity and soluble sugar, especially for exposure to GA of 25 mg L^?1. Soluble sugar content increased significantly especially when exposed to CA for 72 h. When exposed to PA, protein content, and SOD and CAT activities initially increased but over longer treatment time the activities decreased, in contrast to sugar content. Our results suggest that PA exposure for longer periods of time may inhibit catabolism action, while CA exposure could induce more oxide stress than GA or PA. The overall study showed that polyphenol-induced oxidative damage might be responsible for polyphenol inhibition on M. aeruginosa growth. The increases in cellular antioxidant enzymes and soluble sugar may have been to counteract the oxidative stress.     

Effect of soil pH on availability to crops of metals in sewage sludge-treated soils. II. Cadmium uptake by crops and implications for human dietary intake

Appropriate pH-related permissible soil-limit concentrations for cadmium in sewage sludge-treated agricultural soils were estimated from the proportional changes in concentrations of cadmium in potatoes, oats and ryegrass grown on two sludge-amended soils and at different pH values. Implications for potential human dietary intake of cadmium were also assessed. Yields of crops increased with increasing soil pH, probably in response to decreasing uptake of zinc as soil pH value was raised. In general, cadmium concentrations in peeled potato tubers, potato peelings, oat straw and ryegrass decreased as simple linear functions of increasing soil pH over the range of pH values measured (pH 3.9-7.6). Cadmium concentrations in potato peel were particularly sensitive to changing pH conditions, whereas cadmium levels in oat grain were independent of soil pH. On the basis that a highly precautionary approach is adopted in setting soil standards for heavy metals, appropriate permissible concentrations of cadmium in sludge-treated agricultural soil which protect the human food chain were determined as 2.0 and 2.5 mg Cd Kg(-1) for banded pH ranges of 5.0-5.5 and 5.5-6.0, respectively.     

Calcium chloride and calcium bromide aqueous solutions of technical and analytical grade in Lemna bioassay

Saturated water solutions of calcium chloride, calcium bromide and their 1:1 mixture are commonly used as "high density brines" for pressure control in oil wells. To compare the effect of these chemicals of technical grade with the effect of the chemicals of analytical grade the Lemna test was used. The multiplication rate, fresh weight, dry to fresh weight ratio, area covered by plants and chlorophyll content were measured as toxicity parameters. The concentrations of tested chemicals were 0.025, 0.05. 0.075 and 0.1 mol dm(-3). Generally, the chemicals of both technical and analytical grade in concentrations of 0.025 mol dm(-3) stimulated the Lemna minor growth, while tested chemicals in concentrations of 0.05 mol dm(-3) did not affect the growth significantly. The exceptions were results obtained by measuring fresh weight. Most of tested chemicals in concentrations of 0.075 mol dm(-3) and all chemicals in concentrations of 0.1 mol dm(-3) reduced the growth. No major differences between effects of tested chemicals of technical and analytical grade on plant growth were observed, except that tested chemicals of analytical grade in concentrations of 0.1 mol dm(-3) increased dry to fresh weight ratio much stronger than chemicals of technical grade. All tested chemicals in all concentrations increased chlorophyll content. After treatment with chemicals of analytical grade much higher increase of chlorophyll a concentration in comparison to increase of chlorophyll b was noticed, while chemicals of technical grade caused more prominent increase of chlorophyll b.     

凹土-聚合氯化铝复合材料处理含磷废水的研究

以凹土(AG)和聚合氯化铝(PAC)为原料,制备了纳米复合材料AG-PAC复合物(AP),探讨AG与PAC复配比(以质量比计,下同)、AP投加量、反应时间和溶液pH等因素对AP处理低浓度含磷废水的影响.结果表明,在相同的反应条件下,AP对TP的去除效果比单用PAC和AG的去除效果均要好;AG与PAC的最佳复配比为10～...     

Mobility of antimony in soil and its availability to plants

In a historical mining area residual material has been filled on land and these locations are used today as agricultural soils or house gardens. The antimony concentrations in these soils are up to 500 mg/kg. Antimony transfer into 19 vegetable and crop species was investigated. In grain and other storage organs up to 0.09 mg Sb/kg were found, whereas maximum antimony concentrations in shoots and leaves were determined to be 0.34 mg Sb/kg and 2.2 mg Sb/kg, respectively. Despite the high antimony contamination of the soils, concentrations in the investigated plants in general corresponded to concentrations only reported for uncontaminated soils. NH4NO3 extraction of some of the soils indicated that the mobile fraction of antimony present was only 0.06-0.59%. In contrast, in leaves of spinach grown under controlled conditions in soils with a high mobile antimony content an accumulation of the element could be observed: a maximum value of 399 mg Sb/kg was detected, and a correlation between the mobile fraction in the soils and antimony in leaves was found.     

Evaluation of copper availability to plants in copper-contaminated vineyard soils

The repeated use of copper (Cu) fungicides to control vine downy mildew has led to long-term accumulation of Cu in vineyard soils which now raises the issue of the potential bioavailability of Cu for various living organisms including plant species. The bioavailable Cu can be defined as the portion of soil Cu that can be taken up by roots, for a given plant species. In order to evaluate the bioavailability of Cu to plants, a pot experiment was conducted in glasshouse conditions with a crop species (maize) and 12 soils sampled in the upper horizon of 10 vineyard plots (total Cu ranging from 38 to 251 mg kg-1) and two woodland plots (control soils that had not received any Cu application; total Cu amounting to 20-26 mg kg-1). These soils were selected for their diverse physical (large range of particle size distribution) and chemical (from acid to calcareous soils) properties. After 35 days of growth, plant shoots were harvested for analysis. The roots were separated from soil particles for further analysis. The concentrations of Cu in the roots and aerial parts of the maize were then compared with the amounts of Cu extracted from the soil by a range of conventional extractants. Observed Cu concentrations in maize roots which have grown in contaminated vineyard soils were very high (between 90 and 600 mg kg-1), whereas Cu concentrations in the aerial parts varied only slightly and remained low (< 18 mg kg-1). Root Cu concentrations observed for maize increased with increasing total Cu content in the soil and with decreasing soil CEC. Cu accumulation in maize roots may be as high in calcareous soils as in acid soils, suggesting that soil pH had little influence. In the case of the vineyard soils studied, the lack of correlation found for maize between Cu concentrations in roots and in the aerial parts, suggests that an analysis of the aerial parts would not be a good indicator of plant Cu uptake, as it provides no insight into the real amount of Cu transferred from the soil to the plant. For maize, our results show that extraction with organic complexing agents (EDTA, DTPA) and extraction with ammonium acetate seem to provide a reasonably good estimate of root Cu concentration.     

Lead and Cadmium in Precipitation: Their Contribution to Pollution

Atmospheric precipitation samples have been collected at six sites in the London (U.K.) area and at one rural site. Levels of lead and cadmium have been determined and are readily related to local sources of air pollution. A quantitative assessment is made of the metallic pollution resulting from removal of metals from the atmosphere In precipitation and it is compared to the contribution of other pollution pathways.     

Formation and transport of PCDD/Fs in the packed bed of soil containing organic chloride during a thermal remediation process

The authors previously proposed the concept of a new thermal remediation process for particulate/powder materials contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and experimentally verified its validity on the basis of process efficiency. However, contaminees such as soils and fly ashes from waste incinerators often contain a considerable amount of other chlorides, which may act as a main source of chlorine in the formation of PCDD/Fs via thermal processes. The present study aims to examine the formation and transport of PCDD/Fs in the packed bed of soil containing a chloride during the process. Polyvinyl chloride (PVC) polymer was mixed with soil sample as an organic chloride model. A laboratory-scale apparatus was employed as a process simulator. Further, a technique to quench the process was applied to observe the concentration distribution of PCDD/Fs in the solid bed in the vertical direction. The result shows that the PCDFs tend to form dominantly in the high temperature (calcination and/or combustion) zone and are successively trapped in the low temperature (wet) zone. Especially, TeCDF is the most dominant homologue contained in the wet zone and outlet gas. Although PCDD/Fs are once trapped at the wet zone, the concentration of the remediated materials gives fairly low value (1.9 pg/g-dry, 0.04 pg-TEQ/g-dry). It signifies that organic chlorides mingled in the solid contaminee not affect the removal efficiency of PCDD/Fs in the process. Nevertheless, attention should be paid to the potential emission of PCDD/Fs in the outlet gas due to the presence of organic chloride in the soil.     

Evaluation of the capacity of the cyanobacterium Microcystis novacekii to remove atrazine from a culture medium

The bioaccumulation of atrazine and its toxicity were evaluated for the cyanobacterium Microcystis novacekii. Cyanobacterial cultures were grown in WC culture medium with atrazine at 50, 250 and 500 μg L^?1. After 96 hours of exposure, 27.2% of the atrazine had been removed from the culture supernatant. Spontaneous degradation was found to be insignificant (< 9% at 500 μg L^?1), indicating a high efficiency for the bioaccumulation of atrazine by M. novacekii. There were no atrazine metabolites detected in the culture medium at any of the doses studied. The acute toxicity (EC₅₀) of atrazine to the cyanobacterium was 4.2 mg L^?1 at 96 hours demonstrating the potential for M. novacekii to tolerate high concentrations of this herbicide in fresh water environments. The ability of M. novacekii to remove atrazine combined with its tolerance of the pesticide toxicity showed in this study makes it a potential biological resource for the restoration of contaminated surface waters. These findings support continued studies of the role of M. novacekii in the bioremediation of fresh water environments polluted by atrazine.     

Photochemical generation rates of hydroxyl radical in aqueous solutions containing Fe(III)-hydroxy complex

The rates of photochemical generation of hydroxyl radical at 313 nm in aqueous solutions containing ferric ion at acidic pH were measured by the competitive kinetic method using 2-chlorophenol as a test compound and 1-octanol as a radical scavenger. The quantum yield of hydroxyl radical generation calculated from the rates was about 0.02. From the results, it was suggested that this system could be used as a method of wastewater treatment.     

Influence of the current density on the electrochemical treatment of concentrated 1-butyl-3-methylimidazolium chloride solutions on diamond electrodes

This paper focuses on the influence of the current density treatment of a concentrated 1-butyl-3-methylimidazolium chloride (BMImCl) solution on an electrochemical reactor with a boron-doped diamond (BDD) anode. The decrease in the total organic carbon (TOC) and the BMImCl concentration demonstrate the capability of BDD in oxidizing ionic liquids (ILs) and further mineralizing (to CO₂ and NO₃ ^?) more rapidly at higher current densities in spite of the reduced current efficiency of the process. Moreover, the presence of Cl^? led to the formation of oxychlorinated anions (mostly ClO₃ ^? and ClO₄ ^?) and, in combination with the ammonia generated in the cathode from the nitrate reduction, chloramines, more intensely at higher current density. Finally, the analysis of the intermediates formed revealed no apparent influence of the current density on the BMImCl degradation mechanism. The current density presents therefore a complex influence on the IL treatment process that is discussed throughout this paper.     

Growth and photosynthetic responses of the bloom-forming cyanobacterium Microcystis aeruginosa to elevated levels of cadmium

Effects of cadmium (Cd) on the growth and photosynthesis of the bloom-forming cyanobacterium Microcystis aeruginosa Kütz 854 were investigated. The growth was markedly inhibited when it was treated with 4 microM Cd. However, the biomass production was almost not influenced after a prolonged exposure at Cd concentrations < or = 2 microM. Chlorophyll content was more sensitive to Cd toxicity than phycobiliproteins at 0.5 microM Cd. However, the decrease of phycobiliproteins was larger than chlorophyll at the highest Cd concentration. A significant increase of F(v)/F(m) value was observed at Cd concentrations < or = 2 microM. On the other hand, when cells were treated with 4 microM Cd, F(v)/F(m) was significantly increased after 12 h of treatment but decreased after 48 h. The true photosynthesis was decreased with the increase of Cd concentration at 2 h. However, we noticed a recovery when the treatment was prolonged. After 48 h of exposure at the highest Cd concentration, photosynthetic oxygen evolution was markedly inhibited but dark respiration increased by 67%. Cellular Cd contents were augmented with the increase of Cd concentration. To our knowledge, we have demonstrated for the first time that the inhibitory site of Cd in M. aeruginosa is not located at the PSII or PSI level, but is probably situated on the ferredoxin/NADP(+)-oxidoreductase enzyme at the terminal of whole electron transport chain. We noticed also an increase of PSI activity, which is probably linked to the enhancement of cyclic electron transport around PSI. We can conclude that the increase of cyclic electron transport and dark respiration activities, and the decrease of phycobiliproteins might be adaptive mechanisms of M. aeruginosa 854 under high Cd conditions.     

A lysimeter experiment to investigate temporal changes in the availability of pesticide residues for leaching

Leaching of three pesticides (isoproturon, chlorotoluron and triasulfuron) and a tracer (bromide) were determined in four contrasting soils ranging in texture from sandy loam to clay. The compounds were applied to undisturbed columns of soil and four columns for each soil were randomly selected and leached with 24-mm equivalent of water at prescribed time intervals (3, 9, 24, 37 and 57 d after application). A rapid decline in leached loads of isoproturon and chlorotoluron as time from application to irrigation increased was observed in all soils. In contrast, triasulfuron and bromide loads only decreased rapidly in the clay soil. Bromide losses decreased with decreasing clay contents of the soil and therefore with a decrease in structural development. Magnitudes of pesticide losses varied from soil to soil, depending on structural development and the organic carbon content. Pesticide degradation experiments on disturbed and undisturbed soil samples showed that the rapid decline of leached loads with time was faster than could be explained by degradation alone. Five physico-chemical processes are put forward to explain the different patterns of pesticide leached loads observed in the soils: (1) relative extent of preferential flow, (2) sorption capacity of the compounds to the different soils, (3) extent of degradation of the compounds in the soil, (4) variation in sorption kinetics between compounds associated with pesticide diffusion into soil aggregates, and (5) protection of the compounds by a combination of intra-aggregate diffusion and the presence of preferential flow pathways.     

Biomass-derived materials in the remediation of heavy-metal contaminated water: removal of Cadmium(II) and copper(II) from aqueous solutions

Manganese-coated activated carbon (MCAC) and activated carbon were used in batch experiments for the removal of cadmium(II) and copper(II). Results showed that uptake of Cd(II) and Cu(II) was unaffected by increases in pH (3.0 to 8.5) or concentration (1 to 20 mg/L). Increased ionic strength (from 0.001 to 1 M NaNO3), however, significantly affected the uptake of Cd(II); adsorption of Cu(II) was not affected. Freundlich adsorption isotherm results indicated that MCAC possessed higher sorption capacity than activated carbon. Second-order rate constants were found to be 0.0386 for activated carbon and 0.0633 g/mg x min for MCAC for Cd(II) and 0.0774 for AC and 0.1223 g/mg x min for MCAC for Cu(II). Column experiments showed that maximum sorption capacity of MCAC was 39.48 mg/g for Cu(II) and 12.21 mg/g for Cd(II).