Dechlorination of trichloroethylene by Ni/Fe nanoparticles immobilized in PEG/PVDF and PEG/nylon 66 membranes

The highly reactive bimetallic Fe/Ni nanoparticles immobilized in nylon 66 and PVDF membranes were synthesized and characterized for dechlorination of trichloroethylene (TCE) under anoxic conditions. Scanning electron microscopy (SEM) images and electron probe microanalysis (EPMA) elemental maps showed that the distribution of Fe in nylon 66 membrane was uniform and the intensity of Ni layer was higher than that in PVDF membrane. The particle sizes of bimetallic Fe/Ni in PVDF and nylon 66 membranes were 81 ± 12 and 55 ± 14 nm with the Ni layers of 12 ± 3 and 15 ± 2 nm, respectively. Low agglomeration of immobilized Fe/Ni nanoparticles in nylon 66 membrane was observed, presumably attributed to the more multifunctional chelating groups in membrane. A rapid hydrodechlorination of TCE with ethane as the main end product was observed by the immobilized Fe/Ni nanoparticles. The pseudo-first-order rate constants for TCE dechlorination were 6.44 ± 0.32 and 1.66 ± 0.08 h⁻¹ for nylon 66 and PVDF membranes, respectively. In addition, the efficiency and rate of TCE dechlorination increased upon increasing the mass loading of Ni, ranging between 2.5 and 20 wt%, and then decreased when further increased the Ni loading to 25 wt%. In addition, the stability and longevity of the immobilized Fe/Ni nanoparticles was evaluated by repeatedly injecting TCE into the solutions. A rapid and complete dechlorination of TCE by trace amounts of Fe/Ni nanoparticles was observed after 16 cycles of injection within 10 days, indicating that the immobilization of Fe/Ni nanoparticles in the hydrophilic nylon 66 membrane can retain the longevity and high reactivity of nanoparticles towards TCE dechlorination.     

Nitrifier characteristics in submerged membrane bioreactors under different sludge retention times

Three submerged membrane bioreactors (MBRs) were operated continuously for 230 days by feeding with synthetic inorganic wastewater (NH₄⁺-N, 100 mg L⁻¹) under different solids retention times (SRTs. M_30d, 30 days; M_90d, 90 days; M_infinite, no sludge purge) to examine the influence of SRT on nitrification performance and microbial characteristics. All the reactors could oxidize NH₄⁺-N to NO₃⁻-N effectively without accumulation of NO₂⁻-N. M_30d with the shortest SRT showed significantly higher specific ammonium oxidizing rate (SAOR, 0.22 kg NH₄⁺-N kg⁻¹ MLSS day⁻¹) and specific nitrate forming rate (SNFR, 0.13 kg NO₃⁻-N kg⁻¹ MLSS day⁻¹) than the other two MBRs (0.12-0.14 kg NO₃⁻-N kg⁻¹ MLSS day⁻¹ and 0.042-0.068 kg NO₃⁻-N kg⁻¹ MLSS day⁻¹, respectively). Short SRT led to low extracellular polymeric substances (EPS) concentration and long operating cycle. The nitrite oxidizing bacteria (NOB) ratios by both the fluorescence in situ hybridization (FISH) (3.6% for M_30d and 2.1-2.2% for M_90d and M_infinite) and MPN (1.4 × 10⁷ cells g⁻¹ MLSS for M_30d and 6.2 × 10⁵ and 2.7 × 10⁴ cells g⁻¹ MLSS for M_90d and M_infinite) analyses showed that M_30d favored the accumulation of NOB, which was in accordance with the SNFR result. However, the ammonia oxidizing bacteria (AOB) ratios (3.5%, 3.2% and 4.9% for M_30d, M_90d and M_infinite) were not in accordance with the SAOR result. PCR-DGGE, clone library and FISH results showed that the fast-growing Nitrosomonas and Nitrobacter sp. were the dominant AOB and NOB, respectively for M_30d, while considerable slow-growing Nitrosospira and Nitrospira sp. existed in M_infinite, which might be an important reason why M_infinite had a low SAOR and SNFR.     

Adsorption, sedimentation, and inactivation of E. coli within wastewater treatment wetlands

Bacteria fate and transport within constructed wetlands must be understood if engineered wetlands are to become a reliable form of wastewater treatment. This study investigated the relative importance of microbial treatment mechanisms in constructed wetlands treating both domestic and agricultural wastewater. Escherichia coli (E. coli) inactivation, adsorption, and settling rates were measured in the lab within two types of wastewater (dairy wastewater lagoon effluent and domestic septic tank effluent). In situ E. coli inactivation was also measured within a domestic wastewater treatment wetland and the adsorption of E. coli was also measured within the wetland effluent.Inactivation of E. coli appears to be the most significant contributor to E. coli removal within the wastewaters and wetland environments examined in this study. E. coli survived longer within the dairy wastewater (DW) compared to the domestic wastewater treatment wetland water (WW). First order rate constants for E. coli inactivation within the WW in the lab ranged from 0.09 day⁻¹ (d⁻¹) at 7.6 °C to 0.18 d⁻¹ at 22.8 °C. The average in situ rate constant observed within the domestic wetland ranged from 0.02 d⁻¹ to 0.03 d⁻¹ at an average water temperature of 17 °C. First order rate constants for E. coli inactivation within the DW ranged from 0.01 d⁻¹ at 7.7 °C to 0.04 d⁻¹ at 24.6 °C. Calculated distribution coefficients (K_d) were 19,000 mL g⁻¹, 324,000 mL g⁻¹, and 293 mL g⁻¹ for E. coli with domestic septic tank effluent (STE), treated wetland effluent (WLE), and DW, respectively. Approximately 50%, 20%, and 90% of E. coli were “free floating” or associated with particles <5 μm in size within the STE, WLE, and DW respectively. Although 10-50% of E. coli were found to associate with particles >5 μm within both the STE and DW, settling did not appear to contribute to E. coli removal within sedimentation experiments, indicating that the particles the bacteria were associated with had very small settling velocities.The results of this study highlight the importance of wastewater characterization when designing a treatment wetland system for bacterial removal. This study illustrated the level of variability in E. coli removal processes that can be observed within different wastewater, and wetland environments.     

Internal loading of phosphorus in a sedimentation pond of a treatment wetland: effect of a phytoplankton crash

Sedimentation ponds are widely believed to act as a primary removal process for phosphorus (P) in nutrient treatment wetlands. High frequency in-situ P, ammonium (NH₄⁺) and dissolved oxygen measurements, alongside occasional water quality measurements, assessed changes in nutrient concentrations and productivity in the sedimentation pond of a treatment wetland between March and June. Diffusive equilibrium in thin films (DET) probes were used to measure in-situ nutrient and chemistry pore-water profiles. Diffusive fluxes across the sediment-water interface were calculated from the pore-water profiles, and dissolved oxygen was used to calculate rates of primary productivity and respiration. The sedimentation pond was a net sink for total P (TP), soluble reactive P (SRP) and NH₄⁺ in March, but became subject to a net internal loading of TP, SRP and NH₄⁺ in May, with SRP concentrations increasing by up to 41 μM (1300 μl^− 1). Reductions in chlorophyll a and dissolved oxygen concentrations also occurred at this time. The sediment changed from a small net sink of SRP in March (average diffusive flux: − 8.2 μmol m^− 2 day^− 1) to a net source of SRP in June (average diffusive flux: + 1324 μmol m^− 2 day^− 1). A diurnal pattern in water column P concentrations, with maxima in the early hours of the morning, and minima in the afternoon, occurred during May. The diurnal pattern and release of SRP from the sediment were attributed to microbial degradation of diatom biomass, causing reduction of the dissolved oxygen concentration and leading to redox-dependent release of P from the sediment. In June, 2.7 mol-P day^− 1 were removed by photosynthesis and 23 mol-P day^− 1 were supplied by respiration in the lake volume. SRP was also released through microbial respiration within the water column, including the decomposition of algal matter. It is imperative that consideration to internal recycling is given when maintaining sedimentation ponds, and before the installation of new ponds designed to treat nutrient waste.     

Sedimentation of helminth eggs in water

Helminth parasite eggs in low quality water represent health risks when used for irrigation of crops. The settling velocities of helminth eggs (Ascaris suum, Trichuris suis, and Oesophagostomum spp.) and wastewater particles were experimentally determined in tap water and in wastewater using Owen tubes. The settling velocities of eggs in tap water was compared with theoretical settling velocities calculated by Stoke’s law using measurements of size and density of eggs as well as density and viscosity of tap water. The mean settling velocity in tap water of 0.0612 mm s⁻¹ found for A. suum eggs was significantly lower than the corresponding values of 0.1487 mm s⁻¹ for T. suis and 0.1262 mm s⁻¹ for Oesophagostomum spp. eggs. For T. suis and Oesophagostomum spp. eggs the theoretical settling velocities were comparable with the observed velocities in the Owen tubes, while it was three times higher for A. suum eggs. In wastewater, the mean settling velocity for A. suum eggs (0.1582 mm s⁻¹) was found to be different from T. suis (0.0870 mm s⁻¹), Oesophagostomum spp. (0.1051 mm s⁻¹), and wastewater particles (0.0474 mm s⁻¹). This strongly indicates that in low quality water the eggs are incorporated into particle flocs with different settling velocities and that the settling velocity of eggs and particles is closely associated. Our results document that there is a need to differentiate the sedimentation of different types of helminth eggs when assessing the quality of low quality water, e.g. for irrigation usage. The results can also be used to improve existing models for helminth egg removal.     

Characteritization of, and health risks from, polychlorinated dibenzo-p-dioxins/dibenzofurans from incense burned in a temple

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) may cause adverse health effects. However, PCDD/F emissions from burning incense in temples have rarely been addressed. This study investigates PCDD/F emissions from burning incense in a temple. The mean total PCDD/F concentrations were 72.4-82.2 pg Nm^− 3 at two indoor sites; their corresponding mean total PCDD/Fs I-TEQ concentrations (0.24-0.27 pg I-TEQ Nm^− 3) were ~ 11 times that at a background location. In air samples collected from burning incense, OCDFs accounted for approximately 90% of total PCDD/Fs at the two indoor sites and an outdoor site near the temple, while the major PCDD/Fs in incense ash were PCDDs. The total PCDD/F content and toxic equivalent value of incense ash were 617 pg g^− 1 and 1.55 pg I-TEQ g^− 1, respectively. At the three sites inside/outside the temple, the air and ash samples contained the same four primary PCDD/Fs-OCDD, 1,2,3,4,6,7,8-HpCDD, OCDF and 1,2,3,4,6,7,8-HpCDF. The Cl⁻ emission factor, which is related to the PCDD/F formation, from burning incense was 0.454 mg g^− 1. The resultant lifetime average daily dose and cancer risk for temple workers were 0.00964 pg I-TEQ day^− 1 kg^− 1 and 9.64 × 10^− 6, respectively, approximately 2 times that for residents near the temple (0.00489 pg I-TEQ day^− 1 kg^− 1 and 4.89 × 10^− 6, respectively). We suggest that the chlorine content in incense must be regulated, and the high risk of PCDD/F exposure from burning incense for temple workers and visitors should be of concern.     

Size-fractionated (1 → 3)-β-D-glucan concentrations aerosolized from different moldy building materials

Release of submicrometer-sized fungal fragments (< 1.0 μm) was discovered in earlier studies, which investigated the aerosolization of spores from moldy surfaces. However, the contribution of fungal fragments to total mold exposure is poorly characterized. The purpose of this study was to investigate the size-fractionated concentrations of particulate (1 → 3)-β-D-glucan and numbers of particles aerosolized from the surface of artificially mold-contaminated materials using a novel sampling methodology. Aspergillus versicolor and Stachybotrys chartarum were grown on malt extract agar and building materials (ceiling tiles and gypsum board) for one to six months. Fungal particles released from these materials were collected size-selectively by a newly developed Fragment Sampling System, and (1 → 3)-β-D-glucan in air samples was analyzed by Limulus Amebocyte lysate (LAL) assay. The concentrations of (1 → 3)-β-D-glucan varied from 0.4 × 10⁰ to 9.8 × 10² ng m^− 3 in the fragment size and from 1.0 × 10¹ to 4.7 × 10⁴ ng m^− 3 in the spore size range. Numbers of submicrometer-sized particles aerosolized from 6-month old cultures were always significantly higher that those from 1-month old (P < 0.001). This can be attributed to increased dryness on the surface of material samples and an increase in fungal biomass over time. The average fragment to spore ratios both in particle numbers and (1 → 3)-β-D-glucan mass were higher for S. chartarum than for A. versicolor. The results indicate that long-term mold damage in buildings may lead to increased contribution of fragments to the total mold exposure. Therefore, the health impact of these particles may be even greater than that of spores, considering the strong association between numbers of fine particles and adverse health effects reported in other studies. Furthermore, the contribution of fragments may vary between species and appears to be higher for S. chartarum than for A. versicolor.     

Gas-particle partitioning and seasonal variation of polycyclic aromatic hydrocarbons in the atmosphere of Zonguldak, Turkey

Atmospheric concentrations and gas-particle partition coefficients were determined for polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of Zonguldak, Turkey between May 2007 and April 2008. Total concentrations of PAHs ranged from 0.52 ng m^− 3 to 636 ng m^− 3 in the particle phase and from 5.60 ng m^− 3 to 725 ng m^− 3 in the gas phase. The annual mean concentrations of PAHs in the particle and gas phase were found to be 114 ng m^− 3 and 184 ng m^− 3, respectively. Significant seasonal variations of particle and gas phase PAH concentrations were observed with higher levels during cold period. The distribution of PAHs between the particle and gas phase was investigated and it was found that three ring PAHs were associated primarily with the gas phase, four ring PAHs were distributed almost equally between the two phases and five and six ring PAHs were mainly associated with the particle phase. Gas-particle partition coefficients (K_p) of PAHs have been calculated and correlated with their subcooled liquid vapor pressures (P_Lº). The slopes (m_r) varied from − 0.63 to − 0.23 were far from the theoretical value (−1) due to the short distance between the sampling point and the emission sources. The relationships between temperature and gas phase partial pressures of PAHs were examined using the Clausius-Clapeyron equation and the obtained positive slopes indicated that PAH concentrations increased with decreasing air temperature as a result of high dominance of local emissions.     

Effect of COD/SO4ratio and Fe(II) under the variable hydraulic retention time (HRT) on fermentative hydrogen production

The effect of chemical oxygen demand/sulfate (COD/SO₄²⁻) ratio on fermentative hydrogen production using enriched mixed microflora has been studied. The chemostat system maintained with a substrate (glucose) concentration of 15 g COD L⁻¹ exhibited stable H₂ production at inlet sulfate concentrations of 0-20 g L⁻¹ during 282 days. The tested COD/SO₄²⁻ ratios ranged from 150 to 0.75 (with control) at pH 5.5 with hydraulic retention time (HRT) of 24, 12 and 6 h. The hydrogen production at HRT 6 h and pH 5.5 was not influenced by decreasing the COD/SO₄²⁻ ratio from 150 to 15 (with control) followed by noticeable increase at COD/SO₄²⁻ ratios of 5 and 3, but it was slightly decreased when the COD/SO₄²⁻ ratio further decreased to 1.5 and 0.75. These results indicate that high sulfate concentrations (up to 20,000 mg L⁻¹) would not interfere with hydrogen production under the investigated experimental conditions. Maximum hydrogen production was 2.95, 4.60 and 9.40 L day⁻¹ with hydrogen yields of 2.0, 1.8 and 1.6 mol H₂ mol⁻¹ glucose at HRTs of 24, 12 and 6 h, respectively. The volatile fatty acid (VFA) fraction produced during the reaction was in the order of butyrate > acetate > ethanol > propionate in all experiments. Fluorescence In Situ Hybridization (FISH) analysis indicated the presence of Clostridium spp., Clostridium butyricum, Clostridium perfringens and Ruminococcus flavefaciens as hydrogen producing bacteria (HPB) and absence of sulfate reducing bacteria (SRB) in our study.     

Nitrogen transformations and greenhouse gas emissions from a riparian wetland soil: an undisturbed soil column study

Riparian wetlands bordering intensively managed agricultural fields can act as biological filters that retain and transform agrochemicals such as nitrate and pesticides. Nitrate removal in wetlands has usually been attributed to denitrification processes which in turn imply the production of greenhouse gases (CO₂ and N₂O). Denitrification processes were studied in the Salburua wetland (northern Spain) by using undisturbed soil columns which were subsequently divided into three sections corresponding to A-, Bg- and B2g-soil horizons. Soil horizons were subjected to leaching with a 200 mg NO₃⁻ L^− 1 solution (rate: 90 mL day^− 1) for 125 days at two different temperatures (10 and 20 °C), using a new experimental design for leaching assays which enabled not only to evaluate leachate composition but also to measure gas emissions during the leaching process. Column leachate samples were analyzed for NO₃⁻ concentration, NH₄⁺ concentration, and dissolved organic carbon. Emissions of greenhouse gases (CO₂ and N₂O) were determined in the undisturbed soil columns. The A horizon at 20 °C showed the highest rates of NO₃⁻ removal (1.56 mg N-NO₃⁻ kg⁻¹ DW soil day^− 1) and CO₂ and N₂O production (5.89 mg CO₂ kg⁻¹ DW soil day^− 1 and 55.71 μg N-N₂O kg⁻¹ DW soil day^− 1). For the Salburua wetland riparian soil, we estimated a potential nitrate removal capacity of 1012 kg N-NO₃⁻ ha^− 1 year^− 1, and potential greenhouse gas emissions of 5620 kg CO₂ ha^− 1 year^− 1 and 240 kg N-N₂O ha^− 1 year^− 1.     

Measurement of surface mercury fluxes at active industrial gold mines in Nevada (USA)

Mercury (Hg) may be naturally associated with the rock units hosting precious and base metal deposits. Active gold mines are known to have point source releases of Hg associated with ore processing facilities. The nonpoint source release of Hg to the air from the large area (hundreds to thousands of hectares) of disturbed and processed material at industrial open pit gold mines has not been quantified. This paper describes the field data collected as part of a project focused on estimating nonpoint source emissions of Hg from two active mines in Nevada, USA. In situ Hg flux data were collected on diel and seasonal time steps using a dynamic flux chamber from representative mine surfaces. Hg fluxes ranged from < 1500 ng m⁻² day⁻¹ for waste rock piles (0.6-3.5 μg g⁻¹) to 684,000 ng m⁻² day⁻¹ for tailings (2.8-58 μg g⁻¹). Releases were positively correlated with material Hg concentrations, surface grain size, and moisture content. Highest Hg releases occurred from materials under active cyanide leaching and from tailings impoundments containing processed high-grade ore. Data collected indicate that as mine sites are reclaimed and material disturbance ceases, emissions will decline. Additionally local cycling of atmospheric Hg (deposition and re-emission) was found to occur.     

Effects of lanthanum and lanthanum-modified clay on growth, survival and reproduction of Daphnia magna

The novel lanthanum-modified clay water treatment technology (Phoslock^®) seems very promising in remediation of eutrophied waters. Phoslock^® is highly efficient in stripping dissolved phosphorous from the water column and in intercepting phosphorous released from the sediments. The active phosphorous-sorbent in Phoslock^® is the Rare Earth Element lanthanum. A leachate experiment revealed that lanthanum could be released from the clay, but only in minute quantities of 0.13-2.13 μg l⁻¹ for a worst-case Phoslock^® dosage of 250 mg l⁻¹. A life-history experiment with the zooplankton grazer Daphnia magna revealed that lanthanum, up to the 1000 μg l⁻¹ tested, had no toxic effect on the animals, but only in medium without phosphorous. In the presence of phosphorous, rhabdophane (LaPO₄ · nH₂O) formation resulted in significant precipitation of the food algae and consequently affected life-history traits. With increasing amounts of lanthanum, in the presence of phosphate, animals remained smaller, matured later, and reproduced less, resulting in lower population growth rates. Growth rates were not affected at 33 μg La l⁻¹, but were 6% and 7% lower at 100 and 330 μg l⁻¹, respectively, and 20% lower at 1000 μg l⁻¹. A juvenile growth assay with Phoslock^® tested in the range 0-5000 mg l⁻¹, yielded EC₅₀ (NOEC) values of 871 (100) and 1557 (500) mg Phoslock^® l⁻¹ for weight and length based growth rates, respectively. The results of this study show that no major detrimental effects on Daphnia are to be expected from Phoslock^® or its active ingredient lanthanum when applied in eutrophication control.     

Distribution of the solvent-extractable organic compounds in fine (PM1) and coarse (PM1-10) particles in urban, industrial and forest atmospheres of Northern Algeria

The distribution of the solvent-extractable organic components in the fine (PM₁) and coarse (PM_1-10) fractions of airborne particulate was studied for the first time in Algeria. That was done during October 2006 concurrently in a big industrial district, a busy urban area, and a forest national park located in Algiers, Boumerdes, Blida, respectively, which are the three biggest provinces of Northern Algeria. Most of the organic matter identified in both particle size ranges consisted of n-alkanes and n-alkanoic acids, with minor contributions coming from polycyclic aromatic hydrocarbons (PAHs), nitrated polycyclic aromatic hydrocarbons (NPAHs), oxygenated PAHs, and other polar compounds (e.g., caffeine and nicotine). The potential emission sources of airborne contaminants were reconciled by combining the values of n-alkane carbon preference index (CPI) and selected diagnostic ratios of PAHs, calculated in both size ranges. The mean cumulative concentrations of PAHs reached 3.032 ng m^− 3 at the Boumerdes site, urban, 80% of which (i.e. 2.246 ng m^− 3) in the PM₁ fraction, 6.462 ng m^− 3 at Rouiba-Réghaia, industrial district, (5.135 ng m^− 3 or 80% in PM₁), and 0.512 ng m^− 3 at Chréa, forested mountains (0.370 ng m^− 3 or 72% in PM₁). Similar patterns were shown by all organic groups, which resulted overall enriched in the fine particles at the three sites. Carcinogenic and mutagenic potencies associated to PAHs were evaluated by multiplying the concentrations of “toxic” compounds times the corresponding potency factors normalized vs. benzo(a)pyrene (BaP), and were found to be both acceptable.     

Carbo-Iron - An Fe/AC composite - As alternative to nano-iron for groundwater treatment

Carbo-Iron^®1 is a novel colloidal composite consisting of activated carbon colloids (ACC) with a d₅₀ particle size of 0.8 μm and anchored deposits of zero-valent iron clusters. This study discusses the principal material properties of Carbo-Iron colloids (CIC) relevant for groundwater treatment in comparison to commercially available nano-sized zero-valent iron (nZVI). CIC with 10-25 wt% Fe⁰ have been developed and tested in laboratory studies for their suitability as dehalogenation reagent and are especially designed to overcome some limitations known from the utilization of nZVI: CIC combine the sorption properties of ACC and the chemical reactivity of nZVI. In column tests, flushed-in CIC showed an enhanced mobility in sediment material compared to nZVI, without the need for colloid stabilizers. However, adding 1-3 wt-% of carboxymethyl cellulose (CMC) related to CIC as colloid stabilizer was found to assure long-lived stable suspensions under laboratory conditions which may additionally support the already improved mobility of the CIC and the homogeneity of particle deposition on the sediment matrix. The hydrophobic character of the ACC carrier provides a high affinity of CIC to non-aqueous phase liquids (NAPL). In undisturbed flow, the reactive particles are collected at the water-NAPL interface. The reagent accumulation at the organic phase is necessary for a successful source attack.     

Photoassisted reduction of metal ions and organic dye by titanium dioxide nanoparticles in aqueous solution under anoxic conditions

The photoassisted reduction of metal ions and organic dye by metal-deposited Degussa P25 TiO₂ nanoparticles was investigated. Copper and silver ions were selected as the target metal ions to modify the surface properties of TiO₂ and to enhance the photocatalytic activity of TiO₂ towards methylene blue (MB) degradation. X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were used to characterize the crystallinity, chemical species and morphology of metal-deposited TiO₂, respectively. Results showed that the particle size of metal-deposited TiO₂ was larger than that of Degussa P25 TiO₂. Based on XRPD patterns and XPS spectra, it was observed that the addition of formate promoted the photoreduction of metal ion by lowering its oxidation number, and subsequently enhancing the photodegradation efficiency and rate of MB. The pseudo-first-order rate constant (k_obs) for MB photodegradation by Degussa P25 TiO₂ was 3.94 × 10^− 2 min^− 1 and increased by 1.4-1.7 times in k_obs with metal-deposited TiO₂ for MB photodegradation compared to simple Degussa P25 TiO₂. The increase in mass loading of metal ions significantly enhanced the photodegradation efficiency of MB; the k_obs for MB degradation increased from 3.94 × 10^− 2 min^− 1 in the absence of metal ion to 4.64-7.28 × 10^− 2 min^− 1 for Ag/TiO₂ and to 5.14-7.61 × 10^− 2 min^− 1 for Cu/TiO₂. In addition, the electrons generated from TiO₂ can effectively reduce metal ions and MB simultaneously under anoxic conditions. However, metal ions and organic dye would compete for electrons from the illuminated TiO₂.     

Significance and interspecific variability of accumulated trace metal concentrations in Antarctic benthic polychaetes

Trace metals were analysed in polychaetes collected on Polarstern cruise ANT XXI/2 (2003/04) to the Weddell Sea. Pb concentrations were largely less than 1.3 mg kg⁻¹ DW in all samples analysed. Statistical results indicate that the accumulated Cd, Cu and Zn concentrations are related to the feeding guild to which the animals are belonging. Relatively low Cd and Cu concentrations are found in macrophagous carnivores and relatively high concentrations in microphagous detritus feeders. The relationship between Zn concentrations and the feeding guilds of polychaetes is reverse. Cd concentrations range from (median values and interquantile ranges in brackets) 2.6 (1.5-3.2) mg kg⁻¹ DW in the carnivorous Trypanosyllis gigantea to 133 (37-176) mg kg⁻¹ in the microphagous detritus feeder Lanicides bilobata; Cu concentrations from 16 (11-19) mg kg⁻¹ in the carnivorous Antarctinoe spicoides to 40 (23-68) mg kg⁻¹ in the microphagous detritus feeder Phyllocomus crocea and Zn from 89 (69-97) mg kg⁻¹ in the microphagous detritus feeder Isocirrus yungi to 396 (372-404) mg kg⁻¹ in the carnivorous Aglaophamus trissophyllus. Ni is ranging from 3.7 (1.8-6.0) mg kg⁻¹ in Polyeunoa laevis to 34 (20-41) mg kg⁻¹ in A. spicoides, but no significant differences are obvious regarding the feeding guilds. Since information on metals in Antarctic polychaetes is almost completely lacking, our results suggest further studies to clarify the role of feeding in the bioaccumulation of metals in this ecologically important taxonomic group.     

Heavy metals: confounding factors in the response of New Zealand freshwater fish assemblages to natural and anthropogenic acidity

Acidification of freshwaters is a global phenomenon, occurring both through natural leaching of organic acids and through human activities from industrial emissions and mining. The West Coast of the South Island, New Zealand, has both naturally acidic and acid mine drainage (AMD) streams enabling us to investigate the response of fish communities to a gradient of acidity in the presence and absence of additional stressors such as elevated concentrations of heavy metals. We surveyed a total of 42 streams ranging from highly acidic (pH 3.1) and high in heavy metals (10 mg L⁻¹ Fe; 38 mg L⁻¹ Al) to circum-neutral (pH 8.1) and low in metals (0.02 mg L⁻¹ Fe; 0.05 mg L⁻¹ Al). Marked differences in pH and metal tolerances were observed among the 15 species that we recorded. Five Galaxias species, Anguilla dieffenbachii and Anguillaaustralis were found in more acidic waters (pH< 5), while bluegill bullies (Gobiomorphus hubbsi) and torrentfish (Cheimarrichthys fosteri) were least tolerant of low pH (minimum pH 6.2 and 5.5, respectively). Surprisingly, the strongest physicochemical predictor of fish diversity, density and biomass was dissolved metal concentrations (Fe, Al, Zn, Mn and Ni) rather than pH. No fish were detected in streams with dissolved metal concentrations > 2.7 mg L⁻¹ and nine taxa were only found in streams with metal concentrations < 1 mg L⁻¹. The importance of heavy metals as critical drivers of fish communities has not been previously reported in New Zealand, although the mechanism of the metal effects warrants further study. Our findings indicate that any remediation of AMD streams which seeks to enable fish recolonisation should aim to improve water quality by raising pH above ≈ 4.5 and reducing concentrations of dissolved Al and Fe to < 1.0 mg L⁻¹.     

Aerobic degradation of acid orange 7 in a vertical-flow constructed wetland

Biological, aerobic degradation of an azo dye and of the resultant, recalcitrant, aromatic amines in a constructed wetland (CW) was demonstrated for the first time. A vertical-flow CW, planted with Phragmites sp. was fed with 127 mg l⁻¹ of acid orange 7 (AO7) at hydraulic loads of 28, 40, 53 and 108 l m⁻²day⁻¹. Color removal efficiencies of up to 99% clearly demonstrate cleavage of the azo bond, also confirmed by the similar AO7 removal and SO₄²⁻ release rates revealing that adsorption onto the matrix was constant. The positive redox potential at the outlet demonstrates that aerobic conditions were present. Chemical oxygen demand and total organic carbon removal efficiencies of up to 93% were also indicative of AO7 mineralization. The degradation of sulfanilic acid was confirmed by the presence of NO₃⁻, SO₄²⁻ and secondary metabolites, which suggest at least two degradation pathways leading to a common compound, 3-oxoadipate.     

Selenium concentrations of common weeds and agricultural crops grown in the seleniferous soils of northwestern India

The plants grown in seleniferous soils constitute a major source of toxic selenium levels in the food chain of animals and human beings. Greenhouse and field experiments were conducted to study selenium concentrations of weeds, forages and cereals grown on seleniferous soils located between 31.0417° to 31.2175° N and 76.1363° to 76.4147° E in northwestern India. Eleven winter season (November-April) weed plants were grown in the greenhouse in a soil treated with different levels of selenate-Se. Selenium concentrations of weed plants increased progressively with the levels of selenate-Se in soil. The highest Se concentration was recorded by Silene gallica (246 mg kg^− 1) and the lowest by Avena ludoviciana (47 mg kg^− 1) at 2.5 mg Se kg^− 1 soil. A.ludoviciana and Spergula arvensis proved highly tolerant to the presence of 1.25 and 2.5 mg selenate-Se kg^− 1 soil and the remaining weeds were sensitive to Se. Dry matter yield of Se-sensitive weed plants was 25 to 62% of the yield in the no-Se control at 1.25 mg selenate-Se kg^− 1 and 6 to 40% at 2.5 mg selenate-Se kg^− 1 soil. Other symptoms like change in leaf colour and size, burning of leaf tips and margins, and delayed flowering were also observed due to Se. Dry matter yield of Se-sensitive weed plants expressed as percentage of yield in the no-Se control at both the Se levels was inversely correlated with their Se content (r = − 0.731, p < 0.01, N = 17). Among the weed plants grown in seleniferous soils under field situations, Mentha longifolia accumulated the highest Se (365 mg kg^− 1) and Phalaris minor the lowest (34 mg kg^− 1). Among agricultural crops grown on a naturally contaminated soil in the greenhouse, Se concentrations were the highest for oilseed crops (19-29 mg kg^− 1), followed by legumes (6-13 mg kg^− 1) and cereals (2-18 mg kg^− 1). Helianthus annuus among the oilseed crops, A.ludoviciana among the winter season weeds, M.longifolia among the summer season (May-October) weeds and Cirsium arvense among the perennial weeds can be used for phytoremediation of seleniferous soils as these accumulate the highest amounts of Se.