Hydrochemistry of urban groundwater, Seoul, Korea: the impact of subway tunnels on groundwater quality

Hydrogeologic and hydrochemical data for subway tunnel seepage waters in Seoul (Republic of Korea) were examined to understand the effect of underground tunnels on the degradation of urban groundwater. A very large quantity of groundwater (up to 63 million m³ year^− 1) is discharged into subway tunnels with a total length of 287 km, resulting in a significant drop of the local groundwater table and the abandonment of groundwater wells. For the tunnel seepage water samples (n = 72) collected from 43 subway stations, at least one parameter among pathogenic microbes (total coliform, heterotrophic bacteria), dissolved Mn and Fe, NH₄⁺, NO₃⁻, turbidity, and color exceeded the Korean Drinking Water Standards. Locally, tunnel seepage water was enriched in dissolved Mn (avg. 0.70 mg L^− 1, max. 5.58 mg L^− 1), in addition to dissolved Fe, NH₄⁺, and pathogenic microbes, likely due to significant inflow of sewage water from broken or leaking sewer pipes.Geochemical modeling of redox reactions was conducted to simulate the characteristic hydrochemistry of subway tunnel seepage. The results show that variations in the reducing conditions occur in urban groundwater, dependent upon the amount of organic matter-rich municipal sewage contaminating the aquifer. The organic matter facilitates the reduction and dissolution of Mn- and Fe-bearing solids in aquifers and/or tunnel construction materials, resulting in the successive increase of dissolved Mn and Fe. The present study clearly demonstrates that locally significant deterioration of urban groundwater is caused by a series of interlinked hydrogeologic and hydrochemical changes induced by underground tunnels.     

Enhanced effect of HAH on citric acid-chelated Fe(II)-catalyzed percarbonate for trichloroethene degradation

This work demonstrates the impact of hydroxylamine hydrochloride (HAH) addition on enhancing the degradation of trichloroethene (TCE) by the citric acid (CA)-chelated Fe(II)-catalyzed percarbonate (SPC) system. The results of a series of batch-reactor experiments show that TCE removal with HAH addition was increased from approximately 57 to 79% for a CA concentration of 0.1 mM and from 89 to 99.6% for a 0.5 mM concentration. Free-radical probe tests elucidated the existence of hydroxyl radical (HO^•) and superoxide anion radical (O₂ ^•-) in both CA/Fe(II)/SPC and HAH/CA/Fe(II)/SPC systems. However, higher removal rates of radical probe compounds were observed in the HAH/CA/Fe(II)/SPC system, indicating that HAH addition enhanced the generation of both free radicals. In addition, increased contribution of O₂ ^•- in the HAH/CA/Fe(II)/SPC system compared to the CA/Fe(II)/SPC system was verified by free-radical scavengers tests. Complete TCE dechlorination was confirmed based on the total mass balance of the released Cl⁻ species. Lower concentrations of formic acid were produced in the later stages of the reaction for the HAH/CA/Fe(II)/SPC system, suggesting that HAH addition favors complete TCE mineralization. Studies of the impact of selected groundwater matrix constituents indicate that TCE removal in the HAH/CA/Fe(II)/SPC system is slightly affected by initial solution pH, with higher removal rates under acidic and near neutral conditions. Although HCO₃ ⁻ was observed to have an adverse impact on TCE removal for the HAH/CA/Fe(II)/SPC system, the addition of HAH reduced its inhibitory effect compared to the CA/Fe(II)/SPC system. Finally, TCE removal in actual groundwater was much significant with the addition of HAH to the CA/Fe(II)/SPC system. The study results indicate that HAH amendment has potential to enhance effective remediation of TCE-contaminated groundwater.

     

A novel application of H2O2-Fe(II) process for arsenate removal from synthetic acid mine drainage (AMD) water

Batch experiments were carried out to investigate the influences of H₂O₂/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H₂O₂-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H₂O₂/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L⁻¹. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L⁻¹. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H₂O₂-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L⁻¹ in treated solution. The results suggested that the H₂O₂-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.     

Acute and chronic effects of nano- and non-nano-scale TiO2 and ZnO particles on mobility and reproduction of the freshwater invertebrate Daphnia magna

Among the emerging literature addressing the biological effects of nanoparticles, very little information exists, particularly on aquatic organisms, that evaluates nanoparticles in comparison to non-nanocounterparts. Therefore, the potential effects of nano-scale and non-nano-scale TiO₂ and ZnO on the water flea, Daphnia magna, were examined in 48-h acute toxicity tests using three different test media, several pigment formulations – including coated nanoparticles – and a variety of preparation steps. In addition, a 21-d chronic Daphnia reproduction study was performed using coated TiO₂ nanoparticles. Analytical ultracentrifugation analyses provided evidence that the nanoparticles were present in a wide range of differently sized aggregates in the tested dispersions. While no pronounced effects on D. magna were observed for nano-scale and non-nano-scale TiO₂ pigments in 19 of 25 acute (48-h) toxicity tests (EC50 > 100 mg L⁻¹), six acute tests with both nano- and non-nano-scale TiO₂ pigments showed slight effects (EC10, 0.5–91.2 mg L⁻¹). For the nano-scale and non-nano-scale ZnO pigments, the acute 48-h EC50 values were close to the 1 mg L⁻¹ level, which is within the reported range of zinc toxicity to Daphnia. In general, the toxicity in the acute tests was independent of particle size (non-nano-scale or nano-scale), coating of particles, aggregation of particles, the type of medium or the applied pre-treatment of the test dispersions. The chronic Daphnia test with coated TiO₂ nanoparticles demonstrated that reproduction was a more sensitive endpoint than adult mortality. After 21 d, the NOEC for adult mortality was 30 mg L⁻¹ and the NOEC for offspring production was 3 mg L⁻¹. The 21-d EC10 and EC50 values for reproductive effects were 5 and 26.6 mg L⁻¹, respectively. This study demonstrates the utility of evaluating nanoparticle effects relative to non-nano-scale counterparts and presents the first report of chronic exposure to TiO₂ nanoparticles in D. magna.     

Hydroxyiminodisuccinic acid (HIDS): A novel biodegradable chelating ligand for the increase of iron bioavailability and arsenic phytoextraction

The influence of biodegradable chelating ligands on arsenic and iron uptake by hydroponically grown rice seedlings (Oryza sativa L.) was investigated. Even though the growth solution contained sufficient Fe, the growth of rice seedlings gradually decreased up to 76% with the increase of pH of the solution from 7 to 11. Iron forms insoluble ferric hydroxide complexes at neutral or alkaline pH in oxic condition. Chelating ligands produce soluble ‘Fe–ligand complex’ which assist Fe uptake in plants. The biodegradable chelating ligand hydroxyiminodisuccinic acid (HIDS) was more efficient then those of ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic acid (IDS) in the increase of Fe uptake and growth of rice seedling. A total of 79 ± 20, 87 ± 6, 116 ± 15, and 63 ± 18 mg dry biomass of rice seedlings were produced with the addition of 0.5 mM of EDDS, EDTA, HIDS, and IDS in the nutrient solution, respectively. The Fe concentrations in rice tissues were 117 ± 15, 82 ± 8, 167 ± 25, and 118 ± 22 μmol g⁻¹ dry weights when 0.25 mM of EDDS, EDTA, HIDS, and IDS were added to the nutrient solution, respectively. Most of the Fe accumulated in rice tissues was stored in roots after the addition of chelating ligands in the solution. The results indicate that the HIDS would be a potential alternative to environmentally persistent EDTA for the increase of Fe uptake and plant growth. The HIDS also increased As uptake in rice root though its translocation from root to shoot was not augmented. This study reports HIDS for the first time as a promising chelating ligand for the enhancement of Fe bioavailability and As phytoextraction.     

Ultraviolet light-emitting diodes in water disinfection

Background, aim, and scope  The novel system of ultraviolet light-emitting diodes (UV LEDs) was studied in water disinfection. Conventional UV lamps, like mercury vapor lamp, consume much energy and are considered to be problem waste after use. UV LEDs are energy efficient and free of toxicants. This study showed the suitability of LEDs in disinfection and provided information of the effect of two emitted wavelengths and different test mediums to Escherichia coli destruction. Materials and methods  Common laboratory strain of E. coli (K12) was used and the effects of two emitted wavelengths (269 and 276 nm) were investigated with two photolytic batch reactors both including ten LEDs. The effects of test medium were examined with ultrapure water, nutrient and water, and nutrient and water with humic acids. Results  Efficiency of reactors was almost the same even though the one emitting higher wavelength had doubled optical power compared to the other. Therefore, the effect of wavelength was evident and the radiation emitted at 269 nm was more powerful. Also, the impact of background was studied and noticed to have only slight deteriorating effect. In the 5-min experiment, the bacterial reduction of three to four log colony-forming units (CFU) per cubic centimeter was achieved, in all cases. Discussion  When turbidity of the test medium was greater, part of the UV radiation was spent on the absorption and reactions with extra substances on liquid. Humic acids can also coat the bacteria reducing the sensitivity of the cells to UV light. The lower wavelength was distinctly more efficient when the optical power is considered, even though the difference of wavelengths was small. The reason presumably is the greater absorption of DNA causing more efficient bacterial breakage. Conclusions  UV LEDs were efficient in E. coli destruction, even if LEDs were considered to have rather low optical power. The effect of wavelengths was noticeable but the test medium did not have much impact. Recommendations and perspectives  This study found UV LEDs to be an optimal method for bacterial disinfection. The emitted wavelength was found to be an essential factor when using LEDs; thus, care should be taken in selecting the proper LED for maximum disinfection.     

Fenton-like oxidation and mineralization of phenol using synthetic Fe(II)–Fe(III) green rusts

Background, aim, and scope  

In literature, the environmental applications of green rust (GR) have mainly been pointed out through the reduction of inorganic contaminants and the reductive dechlorination of chlorinated organics. However, reactions involving GR for the oxidation and mineralization of organic pollutants remain very scantly described. In this study, the ability of three synthetic Fe(II)–Fe(III) green rusts, GR(CO₃²⁻), GR(SO₄²⁻), and GR(Cl⁻), to promote Fenton-like reaction was examined by employing phenol as a model pollutant. Unlike the traditional Fenton’s reagent (dissolved Fe(II) + H₂O₂), where the pH values have to be lowered to less than 4, the proposed reaction can effectively oxidize the organic molecules at neutral pH and could avoid the initial acidification which may be costly and destructive for the in situ remediation of contaminated groundwater and soils. The green rust reactivity towards the oxidative transformation of phenol was thoroughly evaluated by performing a large kinetic study, chemical analyses, and spectroscopic investigations.     

Sequential coupling of bio-augmented permeable reactive barriers for remediation of 1,1,1-trichloroethane contaminated groundwater

Sequential coupling of high-density luffa sponge (HDLS) immobilized microorganism and permeable reactive barriers (IM Bio-PRBs) was superior to intimate coupling of free microorganism and permeable reactive barriers (FM Bio-PRBs) for remediation of 1,1,1-trichloroethane contaminated groundwater. IM Bio-PRBs had much better performance to removal 1,1,1-trichloroethane (1,1,1-TCA) and prevent the transport of 1,1,1-TCA and inorganic ions (NO₃^?, PO₄^3?, and SO₄^2?). The majority of them were prevented and accumulated in upgradient of IM Bio-PRBs. 1,1,1-TCA and inorganic ions in there contributed to the much faster growth of microorganism in upgradient aquifer. Therefore, the removal of 1,1,1-TCA and consumption of inorganic ions in upgradient of Bio-PRBs played a constructive role in reducing the processing load of following zero-valent iron (ZVI) PRBs and the negative effect of free microorganism cells (biological clogging) and inorganic ions (chemical clogging) on Bio-PRB permeability. In addition, IM Bio-PRBs were more conducive to accelerate the removal of 1,1,1-TCA in long-term remediation and 1,1,1-TCA residual concentration significantly lower than the safety standard of 0.2 mg L^?1. The change of terminal by-products of 1,1,1-TCA contaminated groundwater in Bio-PRBs showed that 1,1,1-TCA could be effectively de-chlorinated and mineralized in Bio-PRBs. The reductant H₂S (prolong the service life of ZVI-PRBs) was much more produced and utilized in IM Bio-PRBs. Taken together, sequentially coupled IM Bio-PRBs had a better overall performance, and its service life could be prolonged. It was a different design and idea to update conventional PRB remediation technology and theory.

     

Embryo toxicity of pesticides and heavy metals to the ramshorn snail, Marisa cornuarietis (Prosobranchia)

An invertebrate embryo toxicity test with the ampullariid snail, Marisa cornuarietis, to assess the toxicity of pesticides and heavy metals recently was established. Snail embryos were treated with atrazine (100, 1000, 10 000, and 30 000 μg/L), imidacloprid (10 000, 25 000, and 50 000 μg/L), Ni²⁺ (0.1, 1, 10, and 100 μg/L) or Zn²⁺ (100, 200, 500, 1000, 2000, and 5000 μg/L). The effect of these substances was examined by monitoring the following endpoints: mortality, formation of tentacles and eyes, heart rate, hatching, and weight after hatching. Effects in term of a significant delay on the formation of both tentacles and eyes were found after treatment with 100 μg/L Ni²⁺ or 200 μg/L Zn²⁺. The heart rate was shown to significantly decrease at 25 000 μg/L imidacloprid or 1000 μg/L Zn²⁺. At 100 μg/L atrazine, 10 μg/L Ni²⁺, or 1000 μg/L Zn²⁺ a significant delay in hatching became visible. No significant mortality was observed for the tested concentrations of atrazine, imidacloprid, or Ni²⁺, while 5000 μg/L Zn²⁺ resulted in 100% mortality after 10 d. The weight of freshly hatched individuals remained unaffected in all treatments. On the basis of the lowest observed effect concentrations (LOECs) recorded, we could show the M. cornuarietis embryo toxicity test (MariETT) to react up to three orders of magnitude more sensitive (for metals) and at least one order of magnitude more sensitive (for the tested organics) than the established Danio rerio embryo test.     

Effect of humate on biological treatment of wastewater containing heavy metals

This paper presents results of investigations on the influence of humic substances (humate, HS) on the biological treatment of wastewater containing heavy metals (Cr, Cu, Fe, Mn, Ni, and Zn). Respirometric studies indicated that the investigated system complied with the Haldane model for inhibitory wastes. Chemical analyses showed that, while the soluble COD removal was high (82%), only 7% of ammonia was oxidized to nitrate. An addition of HS (500 mg L⁻¹) mitigated the inhibitory effect of the wastewater on the returned activated sludge. The system with HS complied with the Monod model for non-inhibitory wastes, and the removal of ammonia and metals was 99% and over 90%, respectively. It is suggested that an application of HS could be beneficial for treatment plants receiving wastewater streams containing heavy metals.     

原位水解生成的羟基氧化铁凝聚吸附除磷效能与机制简

将不同摩尔比Fe³⁺与OH^-（[Fe³⁺]：[OH^-]=1：0、1：1、1：2和1：3）反应获得原位水解生成的羟基氧化铁（in situ FeO_xH_y），研究了具有不同水解程度的羟基氧化铁对凝聚吸附除磷效能与机制。研究显示，In situ FeO_xH_y对磷的去除率随铁投量增大而升高，且均在中性pH范围内具有最佳除磷效果；在相同铁投量条件下，磷去除率随着[OH^-]：[Fe³⁺]的升高而降低；当体系碱度较低时（pH<6），引入OH^-可促进Fe³⁺水解而提高除磷效果。4种羟基氧化铁均可在15 s内可快速吸附磷，且吸附过程符合准二级动力学模型；Freundlich模型均可很好地描述磷在4种羟基氧化铁表面的吸附行为。磷酸盐吸附后，In situ FeO_xH_y表面Zeta电位明显降低，且[Fe³⁺]：[OH^-]为1：0的羟基氧化铁降低最为显著。结合MINITEQ计算软件磷酸盐、铁盐形态分析结果显示，对于碱度较低的体系，通过投加一定量OH^-可促进Fe³⁺水解，进而使得其更易与水中H₂PO₄^-与HPO₄^2-结合，生成具有多核羟基的磷酸铁络合物，进而提高除磷效果。     

Arsenic release from arsenic-bearing Fe-Mn binary oxide: effects of E(h) condition

Ferric and manganese binary oxide (FMBO) has been successfully used to remediate arsenic-polluted river, but there still lacks sufficient data to evaluate its effects on environments. The release behaviors of iron (Fe), manganese (Mn), and arsenic (As) in different E_h ranges were investigated for As-bearing FMBO sediment after remediating As-polluted DaSha River by FMBO. Under high E_h range (+550 to +400 mV), slight dissolution of Fe and Mn, which corresponded to 12.2% and 25.6%, and less than 5% of As release were observed in 336 h. Under lower E_h range (+50 to −100 mV), elevated extent of the dissolution of Mn and Fe were observed, which corresponded to as high as 61.3% and 70.1%. Under such conditions, the dissolution rate of Mn was higher than that of Fe. Furthermore, from the established relationship of As release and the dissolution of Fe and Mn, the release of As seemed dominated by the dissolution of Fe. X-ray photoelectron spectroscopy (XPS) analysis demonstrated the release of Fe, Mn, As(III), and As(V) after sodium ascorbate-treatment, and the re-adsorption of As(V), as indicated from the increased binding energy of As 3d from 44.78 to 45.83 eV. Surface element composition analysis indicated significant decrease of Mn from 3.22% to 0.54%, slight increase of Fe from 12.45% to 13.67%, and elevated ratio of As from 0.11% to 0.32% accordingly. The main reactions of Fe and Mn dissolution and the pathways of As release under different E_h ranges were also proposed.     

Accumulation of elements by edible mushroom species II. A comparison of aluminium,barium and nutritional element contents

The aim of the study was to compare accumulation efficiency of Al, Ba and nutritional elements (Ca, Fe, K, Mg, Mn, Na) exhibited by six edible mushrooms collected in particular regions of Poland during the last 20 years. The studied mushroom species were Boletus edulis, Cantharellus cibarius, Lactarius deliciosus, Leccinum aurantiacum, Suillus luteus and Xerocomus badius. The highest and the lowest concentrations of the elements in tested mushroom species were 11 – 410, 34 – 337, 16785 – 34600, 140 – 607, 12 – 75 and 16 – 143 mg kg^?1d.m., respectively. The highest average concentrations of Al, Mg and Mn were observed in Suillus luteus fruiting bodies, while for Ba, Ca, K and Na it was in Lactarius deliciosus. BCF >1 was found for K and Mg in all tested mushroom species and additionally for the highest Ca and Na concentrations of all tested mushroom species except for C. cibarius and S. luteus, respectively. For the other tested elements (Al, Ba, Fe and Mn) BCF values < 1 were recorded.     

Protection of palak (Beta vulgaris L. var Allgreen) plants from ozone injury by ethylenediurea (EDU): Roles of biochemical and physiological variations in alleviating the adverse impacts

Ameliorative effects of ethylenediurea (N-[2-(2-oxo-1-imidazolinidyl) ethyl]-N′ phenylurea, abbreviated as EDU) against ozone stress were studied on selected growth, biochemical, physiological and yield characteristics of palak (Beta vulgaris L. var Allgreen) plants grown in field at a suburban site of Varanasi, India. Mean eight hourly ozone concentration varied from 52 to 73 ppb which was found to produce adverse impacts on plant functioning and growth characteristics. The palak plants were treated with 300 ppm EDU at 10 days after germination at 10 days interval up to the plant maturity. Lipid peroxidation in EDU treated plants declined significantly as compared to non-EDU treated ones. Significant increment in F_v/F_m ratio in EDU treated plants as compared to non-EDU treated ones was recorded. EDU treated plants showed significant increment in ascorbic acid contents and reduction in peroxidase activity as compared to non-EDU treated ones. As a result of the protection provided by EDU against ozone induced stress on biochemical and physiological characteristics of palak, the morphological parameters also responded positively. Significant increments were recorded in shoot length, number of leaves plant⁻¹, leaf area and root and shoot biomass of EDU treated plants as compared to non-EDU treated ones. Contents of Na, K, Ca, Mg and Fe were higher in EDU treated plants as compared to non-EDU treated ones. The present investigation proves the usefulness of EDU in partially ameliorating ozone injury in ambient conditions.     

Host location behavior of Cotesia plutellae Kurdjumov (Hymenoptera: Braconidae) in ambient and moderately elevated ozone in field conditions

In field O₃-enrichment experiments increased herbivore densities have been reported, which could be due to negatively affected host location behavior of natural enemies. We addressed the impact of doubling background O₃ on the host location of the parasitoid Cotesia plutellae by conducting 24-h trials in an open-air O₃-fumigation system during two consecutive years. Two circles (radii 1.40 and 4.00 m) of Plutella xylostella-infested potted cabbage plants were placed in the O₃ and ambient plots. Female wasps were released into each plot from the center, and observed 5 times over a 24-h period to assess their host location capability. Thereafter, plants were kept in laboratory conditions until larvae pupation to determine parasitism rates. No significant differences were detected between ambient and O₃-enriched environments either in the number of wasps found in the field, or in the percentages of parasitized larvae. This suggests that moderately elevated O₃ will not affect the behavior of this parasitoid.     

Uptake of 17β-estradiol and biomarker responses in brown trout (Salmo trutta) exposed to pulses

In streams, chemicals such as 17β-estradiol (E2) are likely to occur in pulses. We investigated uptake and biomarker responses in juvenile brown trout (Salmo trutta) of 3- or 6-h pulses of concentrations up to 370 ng E2 L⁻¹. Uptake by the fish was estimated from disappearance of E2 from tank water. A single 6-h pulse of 370 ng E2 L⁻¹ increased the plasma vitellogenin concentration, liver Erα- and vitellogenin-mRNA. Exposure to 150-160 ng E2 L⁻¹ for 6 h increased vitellogenin in one experiment but not in another. Two 6-h pulses had a larger effect one pulse. Brown trout in the size range 24-74 g took up E2 linearly with time and exposure concentration with a concentration ratio rate of 20.2 h⁻¹. In conclusion, the threshold for induction of estrogenic effects in juvenile brown trout at short term pulse exposure appears to be in the range 150-200 ng E2 L⁻¹.     

Response of antioxidant enzymes in Nicotiana tabacum clones during phytoextraction of heavy metals

Background, aim, and scope  Tobacco, Nicotiana tabacum, is a widely used model plant for growth on heavy-metal-contaminated sites. Its high biomass and deep rooting system make it interesting for phytoextraction. In the present study, we investigated the antioxidative activities and glutathione-dependent enzymes of different tobacco clones optimized for better Cd and Zn accumulation in order to characterize their performance in the field. Main features  The improved heavy metal resistance also makes the investigated tobacco clones interesting for understanding the plant defense enzyme system in general. Freshly harvested plant material (N. tabacum leaves) was used to investigate the antioxidative cascade in plants grown on heavy metal contaminated sites with and without amendments of different ammonium nitrate and ammonium sulfate fertilizers. Materials and methods  Plants were grown on heavily polluted soils in north-east Switzerland. Leaves were harvested at the field site and directly deep frozen in liquid N₂. Studies were concentrated on the antioxidative enzymes of the Halliwell–Asada cycle, and spectrophotometric measurements of catalase (CAT, EC 1.11.1.6), ascorbate peroxidase (APX, EC 1.11.1.11), superoxide dismutase (SOD, EC 1.15.1.1), glutathione peroxidase (GPX, EC 1.11.1.9), glutathione reductase (GR, EC 1.6.4.2), glutathione S-transferase (GST, EC 2.5.1.18) were performed. Results and discussion  We tried to explain the relationship between fertilizer amendments and the activity of the enzymatic defense systems. When tobacco (N. tabacum) plants originating from different mutants were grown under field conditions with varying fertilizer application, the uptake of cadmium and zinc from soil increased with increasing biomass. Depending on Cd and Zn uptake, several antioxidant enzymes showed significantly different activities. Whereas SOD and CAT were usually elevated, several other enzymes, and isoforms of GST were strongly inhibited. Conclusions  Heavy metal uptake represents severe stress to plants, and specific antioxidative enzymes are induced at the cost of more general reactions of the Halliwell–Asada cycle. In well-supplied plants, the glutathione level remains more or less unchanged. The lack of certain glutathione S-transferases upon exposure to heavy metals might be problematic in cases when organic pollutants coincide with heavy metal pollution. When planning phytoremediation of sites, mixed pollution scenarios have to be foreseen and plants should be selected according to both, their stress resistance and hyperaccumulative capacity.     

Biogeochemistry of two types of permeable reactive barriers, organic carbon and iron-bearing organic carbon for mine drainage treatment: Column experiments

Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe⁰-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon mixture contains about 30% (volume) organic carbon (composted leaf mulch) and 70% (volume) sand and gravel. The Fe⁰-bearing organic carbon mixture contains 10% (volume) zero-valent iron, 20% (volume) organic carbon, 10% (volume) limestone, and 60% (volume) sand and gravel. Simulated groundwater containing 380 ppm sulfate, 5 ppm As, and 0.5 ppm Sb was passed through the columns at flow rates of 64 (the OC column) and 62 (the FeOC column) ml d^− 1, which are equivalent to 0.79 (the OC column) and 0.78 (the FeOC column) pore volumes (PVs) per week or 0.046 m d^− 1 for both columns. The OC column showed an initial sulfate reduction rate of 0.4 µmol g (OC)^− 1 d^− 1 and exhausted its capacity to promote sulfate reduction after 30 PVs, or 9 months of flow. The FeOC column sustained a relatively constant sulfate reduction rate of 0.9 µmol g (OC)^− 1 d^− 1 for at least 65 PVs (17 months). In the FeOC column, the δ³⁴S values increase with the decreasing sulfate concentration. The δ³⁴S fractionation follows a Rayleigh fractionation model with an enrichment factor of 21.6‰. The performance decline of the OC column was caused by the depletion of substrate or electron donor. The cathodic production of H₂ by anaerobic corrosion of Fe probably sustained a higher level of SRB activity in the FeOC column. These results suggest that zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs. A sharp increase in the δ¹³C value of the dissolved inorganic carbon and a decrease in the concentration of HCO₃⁻ indicate that hydrogenotrophic methanogenesis is occurring in the first 15 cm of the FeOC column.     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.     

Impact of glyphosate on the development, fertility and demography of Chrysoperla externa (Neuroptera: Chrysopidae): Ecological approach

Few ecotoxicological studies have used life table analysis to evaluate the toxicity of pesticides on beneficial organisms. This study is the first report of the effect of the herbicide glyphosate on a predator insect, Chrysoperla externa, using a demographic approach. This predator is associated to soybean pests and has a potential role as a biological control agent in the Neotropical Region. The objective of this work was to evaluate the side-effects of glyphosate on the development, fertility and demography of C. externa, treated orally by ingestion of glyphosate-dipped eggs of Sitotroga cerealella in laboratory conditions. The data were analyzed using the age-stage, two-sex life table. Development from third larval instar to pupae and adult longevity were shorter in glyphosate-treatment than in the control. Adult pre-reproductive period was longer in glyphosate-treatment than in the control. Fecundity and fertility were deeply reduced, as well, being fertility greater affected. A high important reduction was registered in all population parameters. Most eggs from glyphosate-treated cohort looked abnormal, smaller than control, dehydrated and became black 2 d after oviposition. In addition, adults developed tumours in the abdomen region at 20 d after emergence, being the effect more drastic in females than males. It is beyond the scope of our study to speculate on the effects of this herbicide on C. externa field populations. However, it seems likely that populations under continuous use of glyphosate would be exposed at greater detrimental effects in the long term.