Efficacy and environmental acceptability of two ballast water treatment chemicals and an alkylamine based-biocide

Ship's ballast waters transport large numbers of organisms which may become invasive in coastal regions. One option to address this problem is the use of biocides as ballast water treatment (BWT). Efficacy and environmental acceptability of three commercial active substances (the BWT biocides Peraclean^® Ocean and Seakleen^®, and alkylamine-based biocide Mexel^® 432/336) were tested against three bacteria species, two vegetative microalgae and one zooplanktonic larva, in 10 and 30 Practical Salinity Unit (PSU) waters. In both salinities, PeraClean^® Ocean was the most effective biocide against bacteria causing > 90% mortality at 20 mg/l, compared with 50 mg/l for Mexel^® 432/336 and > 500 mg/l for Seakleen^®. Regarding zooplankton, Seakleen^® was the most effective chemical causing 90% mortality in 24 h at concentrations < 6 mg/l (LC90_24 h) in both salinities, compared with 23 and 26 mg/l for Mexel^® 432/336 and 370 and 480 mg/l for PeraClean^® Ocean in 10 and 30 PSU, respectively. Similar pattern of efficacy was obtained for microalgae in 30 PSU: effective concentrations inducing 50% growth inhibition in 4 days were ≤ 1.6 mg/l for Seakleen^®, ≤ 10.1 mg/l for Mexel^® 432/336 and ≤ 30.9 mg/l for PeraClean^® Ocean. Our work highlighted that treated waters displayed residual toxicity after 24 h still inducing mortality depending on the organism and biocide. However Mexel^® 432/336 is the only biocide which had no impact on oyster larvae development at effective concentration. Altogether our data showed that Mexel^® 432/336 was the only biocide displaying a broad spectrum efficacy in concentrations < 50 mg/l and not toxic for oyster larvae development at this concentration. However residual toxicity of treated waters for any organism should be taken into account in BWT systems utilising biocides.     

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.     

Biohydrogen production from xylose at extreme thermophilic temperatures (70 °C) by mixed culture fermentation

Biohydrogen production from xylose at extreme thermophilic temperatures (70 °C) was investigated in batch and continuous-mode operation. Biohydrogen was successfully produced from xylose by repeated batch cultivations with mixed culture received from a biohydrogen reactor treating household solid wastes at 70 °C. The highest hydrogen yield of 1.62 ± 0.02 mol-H₂/mol-xylose_consumed was obtained at initial xylose concentration of 0.5 g/L with synthetic medium amended with 1 g/L of yeast extract. Lower hydrogen yield was achieved at initial xylose concentration higher than 2 g/L. Addition of yeast extract in the cultivation medium resulted in significant improvement of hydrogen yield. The main metabolic products during xylose fermentation were acetate, ethanol, and lactate. The specific growth rates were able to fit the experimental points relatively well with Haldane equation assuming substrate inhibition, and the following kinetic parameters were obtained: the maximum specific growth rate (μ_max) was 0.17 h⁻¹, the half-saturation constant (K_s) was 0.75 g/L, and inhibition constant (K_i) was 3.72 g/L of xylose. Intermittent N₂ sparging could enhance hydrogen production when high hydrogen partial pressure (>0.14 atm) was present in the headspace of the batch reactors. Biohydrogen could be successfully produced in continuously stirred reactor (CSTR) operated at 72-h hydraulic retention time (HRT) with 1 g/L of xylose as substrate at 70 °C. The hydrogen production yield achieved in the CSTR was 1.36 ± 0.03 mol-H₂/mol-xylose_sonsumed, and the production rate was 62 ± 2 ml/d·L_reactor. The hydrogen content in the methane-free mixed gas was approximately 31 ± 1%, and the rest was carbon dioxide. The main intermediate by-products from the effluent were acetate, formate, and ethanol at 4.25 ± 0.10, 3.01 ± 0.11, and 2.59 ± 0.16 mM, respectively.     

Temporal analysis of net fluvial methylmercury loading in a dystrophic and a clear water lake

The concentration of methylmercury (MeHg) in aquatic ecosystems is the net result of the highly dynamic abiotic and biotic processes of mercury methylation and demethylation. In this study, we conduct an examination of the net fluvial loading of methylmercury (MeHg_Net = MeHg_Watershed − MeHg_{Lake outflow}) across a 3 year time frame in both a dystrophic lake and an oligotrophic lake. A significant portion of MeHg_Net variance in both lakes could be attributed to a seasonal pattern (11.4%, p = 0.009; oligotrophic, and 27.0%, p < 0.0001; dystrophic) which in both cases, was most correlated with air temperature. The dystrophic lake appeared to be a net source of methylmercury (MeHg_Net = − 1.9 ± 0.3 mg MeHg d^− 1) while the oligotrophic lake appeared to be a net sink (MeHg_Net = 0.4 ± 0.2 mg MeHg d^− 1), indicating that there was net methylation in the dystrophic lake and net demethylation in the oligotrophic lake. Higher MeHg loading to the lakes occurred during the summer and between seasons there was a difference in MeHg_Net of 1.1 ±0.3 mg MeHg d^− 1 and 3.1 ± 0.6 mg MeHg d^− 1. Seasonal patterns of MeHg_Net in the oligotrophic lake lagged behind the dystrophic lake by 39 days. The short term variation in MeHg_Net was dominated by precipitation (t = 2.73, p = 0.008; dystrophic, t = 2.53, p = 0.017; oligotrophic).     

Solar treatment of cork boiling and bleaching wastewaters in a pilot plant

This paper reports on cork boiling and bleaching wastewaters treatment by solar photocatalytic processes, TiO₂/UV and Fe²⁺/H₂O₂/UV (TiO₂-only for bleaching wastewater), in a pilot plant with compound parabolic collectors. The photo-Fenton reaction (k = 0.12 L/kJ_UV, r₀ = 59.4 mg/kJ_UV) is much more efficient that TiO₂ photocatalysis and TiO₂ + S₂O₈²⁻ (k = 0.0024 L/kJ_UV, r₀ = 1.36 mg/kJ_UV), leading to 94% mineralization of the bleaching wastewater after 31.5 kJ_UV/L, consuming 77.1 mM of H₂O₂ (3.0 mmol/kJ_UV) and using 20 mg/L of iron. For the cork boiling wastewater, after a slow initial reaction rate, the DOC degradation curve shows a first-order kinetics behaviour (k = 0.015 L/kJ_UV, r₀ = 20.8 mg/kJ_UV) until 173 kJ_UV/L (≈300 mg C/L). According to the average oxidation state (AOS), toxicity profiles, respirometry and kinetic results obtained in two solar CPCs plants, the optimal energy dose estimated for phototreatment to reach a biodegradable effluent is 15 kJ_UV/L and 114 kJ_UV/L, consuming 33 mM and 151 mM of H₂OT:/PGN/ELSEVIER/WR/web/00007490/₂, achieving almost 49% and 48% mineralization of the wastewaters, respectively for the cork bleaching and boiling wastewaters.     

The effect of free nitrous acid on the anabolic and catabolic processes of glycogen accumulating organisms

Nitrite/Free Nitrous Acid (FNA) has previously been shown to inhibit aerobic and anoxic phosphate uptake by polyphosphate accumulating organisms (PAOs). The inhibitory effect of FNA on the aerobic metabolism of Glycogen Accumulating Organisms (GAOs) is investigated. A culture highly enriched (92 ± 3%) in Candidatus Competibacter phosphatis (hereafter called Competibacter) was used. The experimental data strongly suggest that FNA likely directly inhibits the growth of Competibacter, with 50% inhibition occurring at 1.5 × 10⁻³ mgN-HNO₂/L (equivalent to approximately 6.3 mgN-NO₂⁻/L at pH 7.0). The inhibition is well described by an exponential function. The organisms ceased to grow at an FNA concentration of 7.1 × 10⁻³ mgN-HNO₂/L. At this FNA level, glycogen production, another anabolic process performed by GAOs in parallel to growth, decreased by 40%, while the consumption of polyhydroxyalkanoates (PHAs), the intracellular carbon and energy sources for GAOs, decreased by approximately 50%. FNA likely inhibited either or both of the PHA oxidation and glycogen production processes, but to a much less extent in comparison to the inhibition on growth. The comparison of these results with those previously reported on PAOs suggest that FNA has much stronger inhibitory effects on the aerobic metabolism of PAOs than on GAOs, and may thus provide a competitive advantage to GAOs over PAOs in enhanced biological phosphorus removal (EBPR) systems.     

Anatoxin-a degradation by Advanced Oxidation Processes: Vacuum-UV at 172 nm, photolysis using medium pressure UV and UV/H2O2

Two Advanced Oxidation Processes, namely vacuum-ultraviolet (VUV) photolysis at 172 nm and ultraviolet/hydrogen peroxide (UV/H₂O₂) were investigated for the degradation of anatoxin-a in aqueous solutions. Solutions of anatoxin-a-fumarate were treated with VUV light at 172 nm with a UV dose of 200 mJ/cm², where fumaric acid served as a reference compound for a competition kinetics analysis. The second-order rate constant for the reaction between anatoxin-a and the hydroxyl radical was found to be (5.2 ± 0.3) × 10⁹ M⁻¹ s⁻¹ and was independent of pH, temperature, and initial concentration of anatoxin-a. The direct photolysis of anatoxin-a using a medium pressure (MP) UV lamp was also investigated, in which case a UV dose of 1285 mJ/cm² was required to degrade anatoxin-a by 88% and 50% at concentrations of 0.6 mg/L and 1.8 mg/L of toxin, respectively. Treatment of anatoxin-a with a low pressure (LP) UV lamp in the presence of 30 mg/L of H₂O₂ was examined, where it was found that more than 70% of toxin could be degraded at a UV dose of 200 mJ/cm². The degradation arises from the oxidation of the toxin by hydroxyl radicals. The addition of H₂O₂ clearly enhanced the degradation of anatoxin-a, up to a concentration of 40 mg/L, after which addition of more H₂O₂ had little effect on the degradation kinetics of anatoxin-a. The effect of background constituents in the water on the degradation of anatoxin-a was also investigated using natural and synthetically produced model waters.     

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.     

Interaction of Galaxolide® with the human and trout estrogen receptor-α

Synthetic musks have been detected in sewage effluents, surface waters, and fish tissues where the polycyclic musk compound, HHCB (Galaxolide®) is the dominant compound in those matrices. In the present study, the Galaxolide® formulation was tested in the yeast estrogenicity screening (YES) assay, and also tested in in vitro and in vivo teleost systems to determine whether it interacts with the estrogen receptor as either an agonist or antagonist. In those tests, Galaxolide® did not act as an estrogen agonist, however there was strong evidence of antagonistic activity as Galaxolide® inhibited the estrogenic activity of 17β-estradiol (E2). In the YES assay based on a recombinant strain of yeast containing the human estrogen receptor (i.e. hERα), Galaxolide® inhibited the effects of E2 in a dose-dependent manner (IC50 = 1.63 × 10⁻⁵ M). In a luciferase reporter gene assay based on the rainbow trout estrogen receptor (i.e. rtER) transfected into a rainbow trout gonadal (RTG-2) cell line, the IC50 for the antagonistic effect of Galaxolide® was 2.79 × 10⁻⁹ M. In an in vivo assay based on modulation of vitellogenin in rainbow trout, Galaxolide® i.p. injected into trout at a dose of 3.64 mg/kg caused inhibition of E2-induced vitellogenin production. That dose is within the range of concentrations of Galaxolide® that have been detected in tissues of fish from contaminated locations.     

Molecular hydrogen (H2) emissions from gasoline and diesel vehicles

This study assesses individual-vehicle molecular hydrogen (H₂) emissions in exhaust gas from current gasoline and diesel vehicles measured on a chassis dynamometer. Absolute H₂ emissions were found to be highest for motorcycles and scooters (141 ± 38.6 mg km^− 1), approximately 5 times higher than for gasoline-powered automobiles (26.5 ± 12.1 mg km^− 1). All diesel-powered vehicles emitted marginal amounts of H₂ (∼ 0.1 mg km^− 1). For automobiles, the highest emission factors were observed for sub-cycles subject to a cold-start (mean of 53.1 ± 17.0 mg km^− 1). High speeds also caused elevated H₂ emission factors for sub-cycles reaching at least 150 km h^− 1 (mean of 40.4 ± 7.1 mg km^− 1). We show that H₂/CO ratios (mol mol^− 1) from gasoline-powered vehicles are variable (sub-cycle means of 0.44-5.69) and are typically higher (mean for automobiles 1.02, for 2-wheelers 0.59) than previous atmospheric ratios characteristic of traffic-influenced measurements. The lowest mean individual sub-cycle ratios, which correspond to high absolute emissions of both H₂ and CO, were observed during cold starts (for automobiles 0.48, for 2-wheelers 0.44) and at high vehicle speeds (for automobiles 0.73, for 2-wheelers 0.45). This finding illustrates the importance of these conditions to observed H₂/CO ratios in ambient air. Overall, 2-wheelers displayed lower H₂/CO ratios (0.48-0.69) than those from gasoline-powered automobiles (0.75-3.18). This observation, along with the lower H₂/CO ratios observed through studies without catalytic converters, suggests that less developed (e.g. 2-wheelers) and older vehicle technologies are largely responsible for the atmospheric H₂/CO ratios reported in past literature.     

The effect of pH on N2O production under aerobic conditions in a partial nitritation system

Ammonia-oxidising bacteria (AOB) are a major contributor to nitrous oxide (N₂O) emissions during nitrogen transformation. N₂O production was observed under both anoxic and aerobic conditions in a lab-scale partial nitritation system operated as a sequencing batch reactor (SBR). The system achieved 55 ± 5% conversion of the 1 g NH₄⁺-N/L contained in a synthetic anaerobic digester liquor to nitrite. The N₂O emission factor was 1.0 ± 0.1% of the ammonium converted. pH was shown to have a major impact on the N₂O production rate of the AOB enriched culture. In the investigated pH range of 6.0-8.5, the specific N₂O production was the lowest between pH 6.0 and 7.0 at a rate of 0.15 ± 0.01 mg N₂O-N/h/g VSS, but increased with pH to a maximum of 0.53 ± 0.04 mg N₂O-N/h/g VSS at pH 8.0. The same trend was also observed for the specific ammonium oxidation rate (AOR) with the maximum AOR reached at pH 8.0. A linear relationship between the N₂O production rate and AOR was observed suggesting that increased ammonium oxidation activity may have promoted N₂O production. The N₂O production rate was constant across free ammonia (FA) and free nitrous acid (FNA) concentrations of 5-78 mg NH₃-N/L and 0.15-4.6 mg HNO₂-N/L, respectively, indicating that the observed pH effect was not due to changes in FA or FNA concentrations.     

Skin penetrating abilities and reservoir effects of neat DMF and DMF/water mixtures

This study was set out to determine the skin permeabilities of neat N, N-dimethylformamide (DMF, denoted as DMF_100%) and DMF/water mixtures (including 50% DMF/50% water and 10% DMF/90% water mixtures (v/v), denoted as DMF_50% and DMF_10%, respectively) and to assess their skin reservoir effects on the systemic absorption. The penetration fluxes for DMF_10% and DMF_50% (= 0.015 and 0.126 mg/cm²/h, respectively) were only ~ 1.1%and 15% in magnitude as that of DMF_100% (= 0.872 ± 0.231 mg/cm²/h), respectively. The above results could be because the perturbation effect of the DMF content was much more significant than the rehydration effect of the water content on skin permeability. We found that 85.9%, 96.6% and 98.7% of applied doses were still remaining on the skin surface, 4.98%, 0.838% and 0.181% were still remaining in the skin layer, and 9.09%, 2.61% and 1.17% penetrated through the skin layer after the 24-h exposure for DMF_100%, DMF_50% and DMF_10%, respectively. We found that the half-life (T_1/2) of DMF retaining in the skin layer were 12.3, 4.07 and 1.24 h for DMF_100%, DMF_50% and DMF_10%, respectively. The estimated reservoir effect for DMF_100% (=  34.1%) was higher than that of DMF_50% and DMF_10% (= 27.1% and 14.1%, respectively). The above results suggest that the impact associated with the internal burden of DMF could be prolonged even the external exposure of DMF is terminated, particularly for those dermal contact with DMF/water mixtures with high DMF contents.     

Oxone/Co oxidation as an advanced oxidation process: Comparison with traditional Fenton oxidation for treatment of landfill leachate

In this paper, the application of Fenton and Oxone/Co²⁺ oxidation processes for landfill leachate treatment was investigated. The removal of the chemical oxygen demand (COD), suspended substances (SS) and the color of the landfill leachate by Fenton oxidation to that by Oxone/Co²⁺ oxidation were compared under optimal operational conditions. For Fenton oxidation process, the optimal conditions were determined as: [H₂O₂] = 80 mmol L⁻¹, [H₂O₂]/[Fe²⁺] = 2.0, initial pH = 2.5, reaction temperature = 37.5 ± 1 °C, reaction time = 160 min, number of stepwise addition = 3. Under the given conditions, 56.9% of the COD removal efficiency was achieved, but the SS and the color of the treated landfill leachate increased due to the generation of a large quantity of ferric hydroxide sludge. In reference to Oxone/Co²⁺ oxidation process, the optimal conditions were determined as: [Oxone] = 4.5 mmol L⁻¹, [Oxone]/[Co²⁺] = 10⁴, pH = 6.5, reaction temperature = 30 ± 1 °C, reaction time = 300 min, number of stepwise addition = 7, the COD, SS and the color removal efficiencies were 57.5, 53.3 and 83.3%, respectively. From this work, it can be concluded that Oxone/Co²⁺ oxidation process demonstrated higher degradation efficiencies of the COD, SS and color for landfill leachate treatment than that by Fenton oxidation process. It also suggested that Oxone/Co²⁺ oxidation process could be considered as one of the most promising technologies for practical applicability to treat landfill leachate in large scale. For further improving the efficiency of Oxone/Co²⁺ oxidation process, we proposed that combination of it with other technologies in future such as ultraviolet, ultrasound and biological methods.     

Comparison of chlorine and chloramine in the release of mercury from dental amalgam

The purpose of this project was to compare the ability of chlorine (HOCl/OCl⁻) and monochloramine (NH₂Cl) to mobilize mercury from dental amalgam. Two types of amalgam were used in this investigation: laboratory-prepared amalgam and samples obtained from dental-unit wastewater. For disinfectant exposure simulations, 0.5 g of either the laboratory-generated or clinically obtained amalgam waste was added to 250 mL amber bottles. The amalgam samples were agitated by end-over-end rotation at 30 rpm in the presence of 1 mg/L chlorine, 10 mg/L chlorine, 1 mg/L monochloramine, 10 mg/L monochloramine, or deionized water for intervals of 0 h, 2 h, 4 h, 8 h, and 24 h for the clinically obtained amalgam waste samples and 4 h and 24 h for the laboratory-prepared samples. Chlorine and monochloramine concentrations were measured with a spectrophotometer. Samples were filtered through a 0.45 µm membrane filter and analyzed for mercury with USEPA standard method 245.7. When the two sample types were combined, the mean mercury level in the 1 mg/L chlorine group was 0.020 mg/L (n = 25, SD = 0.008). The 10 mg/L chlorine group had a mean mercury concentration of 0.59 mg/L (n = 25, SD = 1.06). The 1 mg/L chloramine group had a mean mercury level of 0.023 mg/L (n = 25, SD = 0.010). The 10 mg/L chloramine group had a mean mercury level of 0.024 mg/L (n = 25, SD = 0.011). Independent samples t-tests showed that there was a significant difference between the natural log mercury measurements of 10 mg/L chlorine compared to those of 1 mg/L and 10 mg/L chloramine. Changing from chlorine to chloramine disinfection at water treatment plants would not be expected to produce substantial increases in dissolved mercury levels in dental-unit wastewater.     

One year environmental surveillance of rotavirus specie A (RVA) genotypes in circulation after the introduction of the Rotarix® vaccine in Rio de Janeiro, Brazil

Rotavirus specie A (RVA) infection is the leading cause of severe acute diarrhea among young children worldwide. To reduce this major RVA health impact, the Rotarix^® vaccine (GlaxoSmithKline, Rixensart, Belgium) was introduced in the Brazilian Expanded Immunization Program in March 2006 and became available to the entire birth cohort. The aim of this study was to evaluate the spread of RVA in the environment after the introduction of Rotarix^® in Brazil. For this purpose, a Wastewater Treatment Plant (WTP) in Rio de Janeiro was monitored for one year to detect, characterize and discriminate RVA genotypes and identify possible circulation of vaccine strains. Using TaqMan^® quantitative PCR (qPCR), RVA was detected in 100% (mean viral loads from 2.40 × 10⁵ to 1.16 × 10⁷ genome copies (GC)/L) of sewage influent samples and 71% (mean viral loads from 1.35 × 10³ to 1.64 × 10⁵ GC/L) of sewage effluent samples. The most prevalent RVA genotypes were P[4], P[6] and G2, based on VP4 and VP7 classification. Direct nucleotide sequencing (NSP4 fragment) and restriction enzyme digestion (NSP3) analysis did not detect RVA vaccine-like strains from the sewage samples. These data on RVA detection, quantification and molecular characterization highlight the importance of environmental monitoring as a tool to study RVA epidemiology in the surrounding human population and may be useful on ongoing vaccine monitoring programs, since sewage may be a good screening option for a rapid and economical overview of the circulating genotypes.     

Drugs degrading photocatalytically: Kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions

The conversion of the antibiotic ofloxacin and the β-blocker atenolol by means of TiO₂ photocatalysis was investigated. Irradiation was provided by a UVA lamp at 3.37 × 10⁻⁶ einstein/s photon flux, while emphasis was given on the effect of catalyst type and loading (50-1500 mg/L), initial substrate concentration (5-20 mg/L), initial pH (3-10) and the effect of H₂O₂ (0.07-1.4 mM) as an additional oxidant on substrate conversion and mineralization in various matrices (i.e. pure water, groundwater and treated municipal effluent). Conversion was assessed measuring sample absorbance at 288 and 224 nm for ofloxacin and atenolol, respectively, while mineralization measuring the dissolved organic carbon. Degussa P25 TiO₂ was found to be more active than other TiO₂ samples for either substrate degradation, with ofloxacin being more reactive than atenolol. Conversion generally increased with increasing catalyst loading, decreasing initial substrate concentration and adding H₂O₂, while the effect of solution pH was substrate-specific. Reaction rates, following a Langmuir-Hinshelwood kinetic expression, were maximized at a catalyst to substrate concentration ratio (w/w) of 50 and 15 for ofloxacin and atenolol, respectively, while higher ratios led to reduced efficiency. Likewise, high concentrations of H₂O₂ had an adverse effect on reaction, presumably due to excessive oxidant scavenging radicals and other reactive species. The ecotoxicity of ofloxacin and atenolol to freshwater species Daphnia magna was found to increase with increasing substrate concentration (1-10 mg/L) and exposure time (24-48 h), with atenolol being more toxic than ofloxacin. Photocatalytic treatment eliminated nearly completely toxicity and this was more pronounced for atenolol.     

Toxicity of 2,4-dinitrotoluene to terrestrial plants in natural soils

The presence of energetic materials (used as explosives and propellants) at contaminated sites is a growing international issue, particularly with respect to military base closures and demilitarization policies. Improved understanding of the ecotoxicological effects of these materials is needed in order to accurately assess the potential exposure risks and impacts on the environment and its ecosystems. We studied the toxicity of the nitroaromatic energetic material 2,4-dinitrotoluene (2,4-DNT) on alfalfa (Medicago sativa L.), barnyard grass (Echinochloa crusgalli L. Beauv.), and perennial ryegrass (Lolium perenne L.) using four natural soils varying in properties (organic matter, clay content, and pH) that were hypothesized to affect chemical bioavailability and toxicity. Amended soils were subjected to natural light conditions, and wetting and drying cycles in a greenhouse for 13 weeks prior to toxicity testing to approximate field exposure conditions in terms of bioavailability, transformation, and degradation of 2,4-DNT. Definitive toxicity tests were performed according to standard protocols. The median effective concentration (EC₅₀) values for shoot dry mass ranged from 8 to 229 mg kg^− 1, depending on the plant species and soil type. Data indicated that 2,4-DNT was most toxic in the Sassafras (SSL) and Teller (TSL) sandy loam soils, with EC₅₀ values for shoot dry mass ranging between 8 to 44 mg kg^− 1, and least toxic in the Webster clay loam soil, with EC₅₀ values for shoot dry mass ranging between 40 to 229 mg kg^− 1. The toxicity of 2,4-DNT for each of the plant species was significantly (p ≤ 0.05) and inversely correlated with the soil organic matter content. Toxicity benchmark values determined in the present studies for 2,4-DNT weathered-and-aged in SSL or TSL soils will contribute to development of an Ecological Soil Screening Level for terrestrial plants that can be used for ecological risk assessment at contaminated sites.     

Releasing behavior of zinc in recirculated bioreactor landfill

The purpose of this research was to determine the releasing behavior of zinc in municipal solid waste (MSW) in landfill site with respect to refuse and leachate as an inseparable system. Two simulated bioreactor landfills, one with leachate recirculation and the other without, were operated in room temperature for 320 days. Results showed that the content of zinc in MSW could amount to 591.29 ± 31.33-632.14 ± 18.98 µg g ^− 1 dry weight ^− 1 (DW ^− 1). It exceeded the set standard for “Environmental quality standard for soil” (≤ 500 µg g ^− 1 DW ^− 1) and had high potential environmental risk. The releasing behavior of zinc in refuse mainly experienced speciation of solid-Zn, Zn²⁺, ZnHCO₃⁺, ZnCO₃, Zn(OH)⁺, Zn(OH)₂, Zn(NH₃)₄²⁺, ZnS, etc. Zinc in refuse showed behaviors of staggered migration and retention, which corresponded with the degradation process of refuse in bioreactor landfill. The Zn²⁺ concentration in leachate, which varied correspondingly with releasing behavior of zinc in refuse, were 0.75 mg L ^− 1 to 3.13 mg L ^− 1 and had no great difference in landfill with different operation modes (CL and RL). However, the amount of Zn²⁺ leached out from refuse, which accounted for 28.70 mg and 130.67 mg after 320 day's operation, respectively. More attention should be paid to the inseparable system including refuse and leachate together.     

Vertical profiles of aerosol absorption coefficient from micro-Aethalometer data and Mie calculation over Milan

Vertical profiles of aerosol number-size distribution and black carbon (BC) concentration were measured between ground-level and 500 m AGL over Milan. A tethered balloon was fitted with an instrumentation package consisting of the newly-developed micro-Aethalometer (microAeth® Model AE51, Magee Scientific, USA), an optical particle counter, and a portable meteorological station. At the same time, PM_2.5 samples were collected both at ground-level and at a high altitude sampling site, enabling particle chemical composition to be determined. Vertical profiles and PM_2.5 data were collected both within and above the mixing layer. Absorption coefficient (b_abs) profiles were calculated from the Aethalometer data: in order to do so, an optical enhancement factor (C), accounting for multiple light-scattering within the filter of the new microAeth® Model AE51, was determined for the first time. The value of this parameter C (2.05 ± 0.03 at λ = 880 nm) was calculated by comparing the Aethalometer attenuation coefficient and aerosol optical properties determined from OPC data along vertical profiles. Mie calculations were applied to the OPC number-size distribution data, and the aerosol refractive index was calculated using the effective medium approximation applied to aerosol chemical composition. The results compare well with AERONET data.The BC and b_abs profiles showed a sharp decrease at the mixing height (MH), and fairly constant values of b_abs and BC were found above the MH, representing 17 ± 2% of those values measured within the mixing layer. The BC fraction of aerosol volume was found to be lower above the MH: 48 ± 8% of the corresponding ground-level values.A statistical mean profile was calculated, both for BC and b_abs, to better describe their behaviour; the model enabled us to compute their average behaviour as a function of height, thus laying the foundations for valid parametrizations of vertical profile data which can be useful in both remote sensing and climatic studies.     

Measurement and source identification of polycyclic aromatic hydrocarbons (PAHs) in the aerosol in Xi'an, China, by using automated column chromatography and applying positive matrix factorization (PMF)

In this study, we measured polycyclic aromatic hydrocarbons (PAHs) in aerosols in Xi'an, China from 2005 to 2007, by using a modified Soxhlet extraction followed by a clean-up procedure using automated column chromatography followed by HPLC/fluorescence detection. The sources of PAHs were apportioned by using the positive matrix factorization (PMF) method. The PM₁₀ concentration in winter (161.1 ± 66.4 μg m^− 3, n = 242) was 1.5 times higher than that in summer (110.9 ± 34.7 μg m^− 3, n = 248). ΣPAH concentrations, which are the sum of the concentrations of all detected PAHs, in winter (344.2 ± 149.7 ng m^− 3, n = 45) was 2.5 times higher than that in summer (136.7 ± 56.7 ng m^− 3, n = 24) in this study. These strong seasonal variations in atmospheric PAH concentration are possibly due to coal combustion for residential heating. According to the source apportionment with PMF method in this study, the major sources of PAHs in Xi'an are categorized as (1) mobile sources such as vehicle exhaust that constantly contribute to PAH pollution, and (2) stationary sources such as coal combustion that have a large contribution to PAH pollution in winter.