Evidences of non-reactive mercury-selenium compounds generated from cultures of Pseudomonas fluorescens

This work was designed to determine chemically inert mercury-selenium (Hg-Se) compounds formed in a culture of Pseudomonas fluorescens exposed to Hg²⁺ and Se^IV (selenite). To isolate these compounds, different digestion methods were studied and sodium dodecyl sulfate (SDS) lysis was selected. The Hg⁰ and non-reactive Hg were determined in two series of cultures containing 0.0-6.00 μg L⁻¹ Se^IV (0.0-76.0 μmol L⁻¹) in combination with low 5.00 μg L⁻¹ (0.025 μmol L⁻¹) or high 100 μg L⁻¹ (0.500 μmol L⁻¹) Hg²⁺. It was found that Hg⁰ formed in the culture decreased with the increase of initial Se^IV, while the non-reactive Hg increased with the Se^IV. In cultures with low initial [Hg²⁺], a median Se^IV (2.0 μg L⁻¹ or 25.3 μmol L⁻¹) resulted in about 70% of the added Hg²⁺ sequestered as non-reactive Hg, and in culture with high initial Hg²⁺, about 40% was sequestered. P. fluorescens was proved to be indispensible for the formation of the non-reactive Hg-Se compounds. The Hg:Se molar ratio in the non-reactive Hg-Se compounds was close to 1, suggesting the existence of mercuric selenide in cells. Mechanisms for the formation of the non-reactive Hg-Se compounds are proposed.     

Degradation of the emerging contaminant ibuprofen in water by photo-Fenton

In this study the degradation of the worldwide Non-Steroidal Anti-Inflammatory Drug (NSAID) ibuprofen (IBP) by photo-Fenton reaction by use of solar artificial irradiation was carried out. Non-photocatalytic experiments (complex formation, photolysis and UV/Vis-H₂O₂ oxidation) were executed to evaluate the isolated effects and additional differentiated degradation pathways of IBP. The solar photolysis cleavage of H₂O₂ generates hydroxylated-IBP byproducts without mineralization. Fenton reaction, however promotes hydroxylation with a 10% contamination in form of a mineralization. In contrast photo-Fenton in addition promotes the decarboxylation of IBP and its total depletion is observed. In absence of H₂O₂ a decrease of IBP was observed in the Fe(II)/UV-Vis process due to the complex formation between iron and the IBP-carboxylic moiety. The degradation pathway can be described as an interconnected and successive principal decarboxylation and hydroxylation steps. TOC depletion of 40% was observed in photo-Fenton degradation. The iron-IBP binding was the key-point of the decarboxylation pathway. Both decarboxylation and hydroxylation mechanisms, as individual or parallel process are responsible for IBP removal in Fenton and photo-Fenton systems. An increase in the biodegradability of the final effluent after photo-Fenton treatment was observed. Final BOD₅ of 25 mg L⁻¹ was reached in contrast to the initial BOD₅ shown by the untreated IBP solution (BOD₅ < 1 mg L⁻¹). The increase in the biodegradability of the photo-Fenton degradation byproducts opens the possibility for a complete remediation with a final post-biological treatment.     

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.     

Environmental occurrence and degradation of the herbicide n-chloridazon

A sampling campaign was carried out for n-chloridazon (n-CLZ) and its degradation product desphenyl-chloridazon (DPC) in the Hesse region (Germany) during the year 2007: a total of 548 environmental samples including groundwater, surface water and wastewater treatment plant (WWTP) effluent were analysed. Furthermore, aerobic degradation of n-CLZ has been studied utilising a fixed bed bioreactor (FBBR).In surface water, n-CLZ was detected at low concentrations (average 0.01 ± 0.06 μg L⁻¹; maximum 0.89 μg L⁻¹) with a seasonal peak, whereas DPC was present throughout the year at much higher concentrations (average 0.72 ± 0.81 μg L⁻¹; maximum 7.4 μg L⁻¹). Higher n-CLZ concentrations were observed in the North compared with South Hesse, which is ascribed to a higher density of agricultural areas. Furthermore, methylated DPC (Me-DPC), another degradation product, was detected in surface water.In the degradation test, n-CLZ was completely converted to DPC at all concentrations tested (Me-DPC was not formed under the test conditions). DPC was resistant to further degradation during the whole experimental period of 98 days. The results obtained suggest persistence and high dispersion of DPC in the aquatic environment.     

Mineralization enhancement of a recalcitrant pharmaceutical pollutant in water by advanced oxidation hybrid processes

Degradation of the biorecalcitrant pharmaceutical micropollutant ibuprofen (IBP) was carried out by means of several advanced oxidation hybrid configurations. TiO₂ photocatalysis, photo-Fenton and sonolysis - all of them under solar simulated illumination - were tested in the hybrid systems: sonophoto-Fenton (FS), sonophotocatalysis (TS) and TiO₂/Fe²⁺/sonolysis (TFS). In the case of the sonophoto-Fenton process, the IBP degradation (95%) and mineralization (60%) were attained with photo-Fenton (FH). The presence of ultrasonic irradiation slightly improves the iron catalytic activity. On the other hand, total removal of IBP and elimination of more than 50% of dissolved organic carbon (DOC) were observed by photocatalysis with TiO₂ in the presence of ultrasound irradiation (TS). In contrast only 26% of mineralization was observed by photocatalysis with H₂O₂ (TH) in the absence of ultrasound irradiation. Additional results showed that, in the TFS system, 92% of DOC removal and complete degradation of IBP were obtained within 240 min of treatment. The advanced oxidation hybrid systems seems to be a promising alternative for full elimination/mineralization for the recalcitrant micro-contaminant IBP.     

Sublethal toxicity of commercial insecticide formulations and their active ingredients to larval fathead minnow (Pimephales promelas)

Toxic effect concentrations of insecticides are generally determined using the technical grade or pure active ingredient. Commercial insecticide formulations, however, contain a significant proportion (> 90%) of so-called inert ingredients, which may alter the toxicity of the active ingredient(s). This study compares the sublethal toxicity of two insecticides, the pyrethroid bifenthrin, and the phenylpyrazole fipronil, to their commercial formulations, Talstar® and Termidor®. Both insecticides are used for landscape treatment and structural pest control, and can be transported into surface water bodies via stormwater and irrigation runoff. We used larval fathead minnow (Pimephales promelas), to determine effects on growth and swimming performance after short-term (24 h) exposure to sublethal concentrations of pure insecticides and the respective formulations. Significantly enhanced 7 d growth was observed at 10% of the 24 h LC₁₀ (53 μg L⁻¹) fipronil. Swimming performance was significantly impaired at 20% of the 24 h LC₁₀ (0.14 μg L⁻¹) of bifenthrin and 10% of the 24 h LC₁₀ of Talstar® (0.03 μg L⁻¹). Fipronil and Termidor® led to a significant impairment of swimming performance at 142 μg L⁻¹ and 148 μg L⁻¹ respectively, with more pronounced effects for the formulation. Our data shows that based on dissolved concentrations both formulations were more toxic than the pure active ingredients, suggesting that increased toxicity due to inert ingredients should be considered in risk assessments and regulation of insecticides.     

Amoxicillin degradation at ppb levels by Fenton's oxidation using design of experiments

A central composite factorial design methodology was employed to optimise the amoxicillin degradation using the Fenton's oxidation treatment. In this study, the variables considered for the process optimisation were the hydrogen peroxide and ferrous ion initial concentrations and the temperature, for an antibiotic concentration of 450 μg L^− 1 at pH = 3.5. This methodology also allowed assessing and identifying the effects of the different factors studied and their interactions in the process response. An appropriate quadratic model was developed in order to plot the response surface and contour curves, which was used to perform the process optimisation. From this study, it was concluded that ferrous ion concentration and temperature were the variables that most influenced the response. Under the optimal conditions (hydrogen peroxide concentration = 3.50-4.28 mg L^− 1, ferrous ion concentration = 254-350 μg L^− 1 and temperature = 20-30 °C), it was possible to achieve total amoxicillin degradation after 30 min of reaction.     

Oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol by means of Fe(III)-homogeneous photocatalysis and algal toxicity assessment of the treated solutions

Chlorophenols are used worldwide as broad-spectrum biocides and fungicides. They have half-life times in water from 0.6 to 550 h and in sediments up to 1700 h and, due to their numerous origins, they can be found in wastewaters, groundwaters or soils. Moreover, chlorophenols are not readily biodegradable.Recently, classic Advanced Oxidation Processes (AOP) have been proposed for their abatement in an aqueous solution. This paper investigates the oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol, at starting concentrations of 6.1 · 10⁻⁵ mol L⁻¹, in aqueous solutions through Fe(III)/O₂ homogeneous photocatalysis under UV light (303 ÷ 366 nm). The Fe(III)/O₂ homogeneous photocatalysis is less expensive than using H₂O₂ due to the capability of Fe(III) to produce OH radicals, if irradiated with an UVA radiation, and of oxygen to re-oxidize ferrous ions to ferric ones when dissolved in solution. The results show that the best working conditions, for both compounds, are found for pH = 3.0 and initial Fe(III) concentration equal to 1.5·10⁻⁴ mol L⁻¹ although the investigated oxidizing system can be used even at pH close to 4.0 but with slower abatement kinetics. Toxicity assessment on algae indicates that treated solutions of 2,4-dichlorophenol are less toxic on algae Pseudokirchneriella subcapitata if compared to not treated solutions whereas in the case of 3,4-dichlorophenol only the samples collected during the runs at 20 and 60 min are capable of inhibiting the growth of the adopted organism.The values of the kinetic constant for the photochemical re-oxidation of iron (II) to iron (III) and for HO attack to intermediates are evaluated by a mathematical model for pH range of 2.0-3.0 and initial Fe(III) concentrations range of 1.5 · 10⁻⁵-5.2 · 10⁻⁴ mol L⁻¹.     

Removal of diatrizoate with catalytically active membranes incorporating microbially produced palladium nanoparticles

There is an increasing concern about the fate of iodinated contrast media (ICM) in the environment. Limited removal efficiencies of currently applied techniques such as advanced oxidation processes require more performant strategies. The aim of this study was to establish an innovative degradation process for diatrizoate, a highly recalcitrant ICM, by using biogenic Pd nanoparticles as free suspension or immobilized in polyvinylidene fluoride (PVDF) and polysulfone (PSf) membranes. As measured by HPLC-UV, the removal of 20 mg L⁻¹ diatrizoate by a 10 mg L⁻¹ Pd suspension was completed after 4 h at a pH of 10. LC-MS analysis provided evidence for the sequential hydrodeiodination of diatrizoate. Pd did not lose its activity after incorporation in the PVDF and PSf matrix and the highest activity (k_cat = 30.0 ± 0.4 h⁻¹ L g⁻¹ Pd) was obtained with a casting solution of 10% PSf and 500 mg L⁻¹ Pd. Subsequently, water containing 20 mg L⁻¹ diatrizoate was treated in a membrane contactor, in which the water was supplied at one side of the membrane while hydrogen was provided at the other side. In a fed batch configuration, a removal efficiency of 77% after a time period of 48 h was obtained. This work showed that membrane contactors with encapsulated biogenic nanoparticles can be instrumental for treatment of water contaminated with diatrizoate.     

A Fenton-like degradation mechanism for 1,4-dioxane using zero-valent iron (Fe) and UV light

In this study, the degradation mechanism of 1,4-dioxane using zero-valent iron (Fe⁰) in the presence of UV light was investigated kinetically. The degradation of 1,4-dioxane in Fe⁰-only, photolysis, and combined Fe⁰ and UV reactions followed the kinetics of a pseudo-first-order model. The degradation rate constant (19 × 10⁻⁴ min⁻¹) in the combined reaction with UV-C (4.2 mW cm⁻²) and Fe⁰ (5 mg L⁻¹) was significantly enhanced compared to Fe⁰-only (4.8 × 10⁻⁴ min⁻¹) and photolytic reactions (2.25 × 10⁻⁴ min⁻¹), respectively. The removal efficiency of 1,4-dioxane in combined reaction with Fe⁰ and UV within 4 h was enhanced by increasing UV intensity at UV-C region (34% at 4.2 mW cm⁻² and 89% at 16.9 mW cm⁻²) comparing with the removal in the combined reaction with Fe⁰ and UV-A (29% at 2.1 mW cm⁻², and 33% at 12.6 mW cm⁻²). It indicates that 1,4-dioxane was degraded mostly by OH radicals in the combined reaction. The degradation patterns in both Fe⁰-only and combined reactions were well fitted to the Langmuir-Hinshelwood model, implying that adsorption as well as the chemical reaction occurred. The transformation of Fe⁰ to Fe²⁺ and Fe³⁺ was observed in the Fe⁰-only and combined reactions, and the transformation rate of Fe⁰ was improved by UV irradiation. Furthermore, the reduction of Fe³⁺ was identified in the combined reaction, and the reduction rate was enhanced by an increase of UV energy. Our study demonstrated that the enhancement of 1,4-dioxane removal rate occurred via an increased supply of OH radicals from the Fenton-like reaction induced by the photolysis of Fe⁰ and H₂O, and with producing less sludge.     

Formation of bromoform in irradiated titanium dioxide suspensions with varying photocatalyst, dissolved organic carbon and bromide concentrations

We report the formation of bromoform in TiO₂ suspensions (P25) under simulated solar UV irradiation at different concentrations of photocatalyst (0.5-1.5 g L⁻¹) as well as initial concentrations of bromide ions (1-3 mg L⁻¹) and 2,4-dihydroxybenzoic acid (2-10 mg L⁻¹). The extent of bromoform formation (3-17 μg L⁻¹) was most strongly affected by the amount of photocatalyst present and by the initial bromide concentration, increasing either of which leads to increased bromoform formation. Important interaction effects were observed when simultaneously increasing the concentrations of TiO₂ and bromide as well as of bromide and DHBA. The time it takes for bromoform to appear in measurable concentrations in the irradiated TiO₂ suspensions was between 10 and 90 min and most strongly depended on the initial concentration of dissolved organic carbon present in the suspensions, along with the amount of photocatalyst, also in interaction with the initial bromide concentration.     

Kinetics and mechanism for degradation of dichlorvos by permanganate in drinking water treatment

The degradation kinetics and mechanism of dichlorvos by permanganate during drinking water treatment were investigated. The reaction of dichlorvos with permanganate was of second-order overall with negligible pH dependence and an activation energy of 29.5 kJ·mol⁻¹. At pH 7.0 and 25 °C, the rate constant was 25.2 ± 0.4 M⁻¹ s⁻¹. Dichlorvos was first degraded to trimethyl phosphate (TMP) and dimethyl phosphate (DMP) simultaneously which approximately accounted for <5% and ≥95% with respect to phosphorus mass, respectively. Further oxidation of DMP generated a final byproduct, monomethyl phosphate (MMP). MMP was for the first time identified as a major byproduct in chemical oxidation of dichlorvos. The kinetic model based on degradation mechanism and determined reaction rate constants allowed us to predict the evolution of dichlorvos and its byproduct concentrations during permanganate pre-oxidation process at water treatment plants. These results suggest that even though the dichlorvos concentration in surface water complies with the surface water quality standards of China (50 μg L⁻¹), its concentration after conventional water treatment will most probably exceed the drinking water quality standards (1 μg L⁻¹). Moreover, luminescent bacteria test shows that the acute toxicity of dichlorvos solution evidently increased after permanganate oxidation.     

Biodegradability enhancement of a pesticide-containing bio-treated wastewater using a solar photo-Fenton treatment step followed by a biological oxidation process

This work proposes an efficient combined treatment for the decontamination of a pesticide-containing wastewater resulting from phytopharmaceutical plastic containers washing, presenting a moderate organic load (COD = 1662-1960 mg O₂ L⁻¹; DOC = 513-696 mg C L⁻¹), with a high biodegradable organic carbon fraction (81%; BOD₅ = 1350-1600 mg O₂ L⁻¹) and a remaining recalcitrant organic carbon mainly due to pesticides. Nineteen pesticides were quantified by LC-MS/MS at concentrations between 0.02 and 45 mg L⁻¹ (14-19% of DOC). The decontamination strategy involved a sequential three-step treatment: (a) biological oxidation process, leading to almost complete removal of the biodegradable organic carbon fraction; (b) solar photo-Fenton process using CPCs, enhancing the bio-treated wastewater biodegradability, mainly due to pesticides degradation into low-molecular-weight carboxylate anions; (c) and a final polishing step to remove the residual biodegradable organic carbon, using a biological oxidation process. Treatment performance was evaluated in terms of mineralization degree (DOC), pesticides content (LC-MS/MS), inorganic ions and low-molecular-weight carboxylate anions (IC) concentrations. The estimated phototreatment energy necessary to reach a biodegradable wastewater, considering pesticides and low-molecular-weight carboxylate anions concentrations, Zahn-Wellens test and BOD₅/COD ratio, was only 2.3 kJ_UV L⁻¹ (45 min of photo-Fenton at a constant solar UV power of 30 W m⁻²), consuming 16 mM of H₂O₂, which pointed to 52% mineralization and an abatement higher than 86% for 18 pesticides. The biological oxidation/solar photo-Fenton/biological oxidation treatment system achieved pesticide removals below the respective detection limits and 79% mineralization, leading to a COD value lower than 150 mg O₂ L⁻¹, which is in agreement with Portuguese discharge limits regarding water bodies.     

Influence of pharmaceutical residues on the structure of activated sludge bacterial communities in wastewater treatment bioreactors

Concern is growing over contamination of the environment with pharmaceuticals because of their widespread use and incomplete removal during wastewater treatment, where microorganisms drive the key processes. The influence of pharmaceuticals on bacterial community structure in activated sludge was assessed in small-scale wastewater treatment bioreactors containing different concentrations (5, 50, 200 and 500 μg L⁻¹) of several commonly used pharmaceuticals (ibuprofen, naproxen, ketoprofen, diclofenac and clofibric acid). T-RFLP analyses of the bacterial 16S rRNA genes indicated a minor but consistent shift in the bacterial community structure in the bioreactor R50 supplied with pharmaceuticals at a concentration of 50 μg L⁻¹, compared to the control reactor R0, which was operated without addition of pharmaceuticals. In the reactors operated with higher concentrations of pharmaceuticals, a greater structural divergence was observed. Bacterial community composition was further investigated by preparation of two clone libraries of bacterial 16S rRNA genes from reactors R0 and R50. Most clones in both libraries belonged to the Betaproteobacteria, among which Thauera, Sphaerotilus, Ideonella and Acidovorax-related spp. dominated. Nitrite-oxidizing bacteria of the genus Nitrospira sp., which are key organisms for the second stage of nitrification in wastewater treatment plants, were found only in the clone library of the reactor without pharmaceuticals. In addition, diversity indices were calculated for the two clone libraries, indicating a reduced diversity of activated sludge bacterial community in the reactor supplied with 50 μg L⁻¹ of each of selected pharmaceuticals.     

Determination of arsenic leaching from glazed and non-glazed Turkish traditional earthenware

Glazed and non-glazed earthenware is traditionally and widely used in Turkey and most of the Mediterranean and the Middle East countries for cooking and conservation of foodstuff. Acid-leaching tests have been carried out to determine whether the use of glazed and non-glazed earthenware may constitute a human health hazard risk to the consumers. Earthenware was leached with 4% acetic acid and 1% citric acid solutions, and arsenic in the leachates was measured using hydride generation atomic absorption spectrometry. Arsenic concentrations in the leach solution of non-glazed potteries varied from 30.9 to 800 μg L^− 1, while the glazed potteries varied generally from below the limit of detection (0.5 μg L^− 1) to 30.6 μg L^− 1, but in one poorly glazed series it reached to 110 μg L^− 1. Therefore, the risk of arsenic poisoning by poorly glazed and non-glazed potteries is high enough to be of concern. It appears that this is the first study reporting arsenic release from earthenware into food.     

Degradation of fifteen emerging contaminants at μg L initial concentrations by mild solar photo-Fenton in MWTP effluents

The degradation of 15 emerging contaminants (ECs) at low concentrations in simulated and real effluent of municipal wastewater treatment plant with photo-Fenton at unchanged pH and Fe = 5 mg L⁻¹ in a pilot-scale solar CPC reactor was studied. The degradation of those 15 compounds (Acetaminophen, Antipyrine, Atrazine, Caffeine, Carbamazepine, Diclofenac, Flumequine, Hydroxybiphenyl, Ibuprofen, Isoproturon, Ketorolac, Ofloxacin, Progesterone, Sulfamethoxazole and Triclosan), each with an initial concentration of 100 μg L⁻¹, was found to depend on the presence of CO₃²⁻ and HCO₃⁻ (hydroxyl radicals scavengers) and on the type of water (simulated water, simulated effluent wastewater and real effluent wastewater), but is relatively independent of pH, the type of acid used for release of hydroxyl radicals scavengers and the initial H₂O₂ concentration used. Toxicity tests with Vibrio fisheri showed that degradation of the compounds in real effluent wastewater led to toxicity increase.     

Responses of streams in central Appalachian Mountain region to reduced acidic deposition—Comparisons with other regions in North America and Europe

Data from 5 wet deposition stations and 21 streams during 1980-2006 were analyzed to investigate chemical responses of streams to reduced acidic deposition in the central Appalachian Mountain region of West Virginia, USA. Wet deposition of acidic anions (i.e., sulfate, nitrate, and chloride) and hydrogen ions decreased significantly during the studied time period. Stream sulfate showed a delayed response to the reduced acidic deposition, and showed a decrease in the 2000s (− 5.54 µeq L^− 1 yr^− 1) and the whole period (− 0.49 µeq L^− 1 yr^− 1). No significant trend of stream nitrate + nitrite and chloride was observed. Stream alkalinity increased in the 1990s (+ 23.33 µeq L^− 1 yr^− 1) and the whole period (+ 7.26 µeq L^− 1 yr^− 1). Stream hydrogen ions decreased in the 1990s (− 0.002 µeq L^− 1 yr^− 1), 2000s (− 0.001 µeq L^− 1 yr^− 1), and the whole period (− 0.001 µeq L^− 1 yr^− 1). Compared with most acidic streams and lakes in the United States and Europe, a lower decreasing rate of hydrogen ions and higher increasing rate of alkalinity were observed in the alkaline West Virginian streams in the 1990s. However, due to their initial negative or zero alkalinity values, those acidic streams showed a higher percent increase in alkalinity than that in the alkaline West Virginian streams (from 800 µeq L^− 1 yr^− 1 to 1200 µeq L^− 1 yr^− 1). Total aluminum in the West Virginian streams decreased in the 1990s (− 0.67 µmol L^− 1 yr^− 1) and the whole period (− 0.22 µmol L^− 1 yr^− 1). The current study advanced our understanding of streams' responses to the reduced acidic deposition in the Mid-Appalachians since the passage of the 1970 and 1990 Amendments to the United States Clean Air Act (US CAAA).     

An improved system for the control of dissolved oxygen in freshwater aquaria

A system for the removal and control of dissolved oxygen (DO) from freshwater was designed and constructed with aquarium-type fish studies in mind. Degassed water was obtained using a partial vacuum of −14 psi, and DO regulated at an aquarium scale using electronically controlled aeration with timed partial water renewal. The degassing system was capable of producing water with ∼1.7 mg L⁻¹ DO within 10 min of operation, and 0.55 mg L⁻¹ after 2 h. The control system was capable of maintaining DO levels of ca 0.8 mg L⁻¹ over 48 h in the absence of aeration and further capable of precisely controlling DO levels as low as 1.16±0.002 mg L⁻¹ (mean±SEM) with aeration over a 48 h period.     

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.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.