Perfluorinated and other persistent halogenated organic compounds in European shag (Phalacrocorax aristotelis) and common eider (Somateria mollissima) from Norway: A suburban to remote pollutant gradient

Samples of two marine bird species, European shag (Phalacrocorax aristotelis) and common eider (Somateria mollissima) sampled at a remote coastal site in Norway were analysed for POPs and PFCs. Additionally samples of common eider were analysed from two other locations in Norway, representing a gradient from “densely populated” to “remote”. The variety, concentration and distribution of lipophilic POPs in comparison to PFCs were investigated. PCBs were the dominating group of contaminants in the analysed egg samples. Shag eggs had median sumPCBs levels of 4580 ng/g l.w. in 2004. Six different PBDE congeners could be detected in the shag eggs. BDE 47 and 100 were the main contributors with 24 and 27 ng/g l.w. respectively, sumPBDEs was 90 ng/g l.w. Relatively high concentrations of chlordanes were found with a total sum of 903 ng/g l.w. Of other OCs, toxaphene 26 and 52 together (sum 657 ng/g l.w.) and HCB (165 ng/g l.w.) were contributing majorly to the egg burden. Sum HCHs were low; only 54 ng/g l.w. PFOS was the main PFC in egg, plasma and liver samples. Similar median levels of 29, 32 and 27 ng/g w.w. were observed. PFOSA, PFHxS, and PFDcA were observed additionally in all shag samples at minor concentrations with the exception of elevated levels observed in liver for PFOSA and PFDcA with median levels of 7.6 and 7.9 ng/g w.w., respectively. In common eider eggs, the POP concentrations decreased up to 1/8th along the sampled spatial gradient from suburban to remote. Of the 9 detected PFCs, PFOS dominated all samples by one order of magnitude, followed by PFOA. SumPFC concentrations were twice as high at the two fjord sites compared to the remote site. Shorter chained PFCAs like PFOA and PFNA could be detected in the eider eggs whilst being absent in shag eggs.     

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.     

Bacterial responses to Cu-doped TiO2 nanoparticles

The toxicity of Cu-doped TiO₂ nanoparticles (NPs, 20 nm), synthesized by a flame aerosol reactor, to Mycobacterium smegmatis and Shewanella oneidensis MR-1, is the primary focus of this study. Both doped and non-doped TiO₂ NPs (20 nm) tended to agglomerate in the medium solution, and therefore did not penetrate into the cell and damage cellular structures. TiO₂ particles (< 100 mg/L) did not apparently interfere with the growth of the two species in aqueous cultures. Cu-doped TiO₂ NPs (20 mg/L) significantly reduced the M. smegmatis growth rate by three fold, but did not affect S. oneidensis MR-1 growth. The toxicity of Cu-doped TiO₂ NPs was driven by the release of Cu²⁺ from the parent NPs. Compared to equivalent amounts of Cu²⁺, Cu-doped TiO₂ NPs exhibited higher levels of toxicity to M. smegmatis (P-value < 0.1). Addition of EDTA in the culture appeared to significantly decrease the anti-mycobacterium activity of Cu-doped TiO₂ NPs. S. oneidensis MR-1 produced a large amount of extracellular polymeric substances (EPS) under NP stress, especially extracellular protein. Therefore, S. oneidensis MR-1 was able to tolerate a much higher concentration of Cu²⁺ or Cu-doped TiO₂ NPs. S. oneidensis MR-1 also adsorbed NPs on cell surface and enzymatically reduced ionic copper in culture medium with a remediating rate of 61 µg/(liter?OD₆₀₀? hour) during its early exponential growth phase. Since the metal reducing Shewanella species can efficiently “clean” metal-oxide NPs, the activities of such environmentally relevant bacteria may be an important consideration for evaluating the ecological risk of metal-oxide NPs.     

Enhanced nitrogen and phosphorus removal from eutrophic lake water by Ipomoea aquatica with low-energy ion implantation

Ipomoea aquatica with low-energy N⁺ ion implantation was used for the removal of both nitrogen and phosphorus from the eutrophic Chaohu Lake, China. The biomass growth, nitrate reductase and peroxidase activities of the implanted I. aquatica were found to be higher than those of I. aquatica without ion implantation. Higher NO₃-N and PO₄-P removal efficiencies were obtained for the I. aquatica irradiation at 25 keV, 3.9 × 10¹⁶ N⁺ ions/cm² and 20 keV 5.2 × 10¹⁶ N⁺ ions/cm², respectively (p < 0.05). Moreover, the nitrogen and phosphorus contents in the plant biomass with ion implantation were also greater than those of the controls. I. aquatica with ion implantation was directly responsible for 51-68% N removal and 54-71% P removal in the three experiments. The results further confirm that the ion implantation could enhance the growth potential of I. aquatica in real eutrophic water and increase its nutrient removal efficiency. Thus, the low-energy ion implantation for aquatic plants could be considered as an approach for in situ phytoremediation and bioremediation of eutrophic waters.     

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.     

Degradation models and ecotoxicity in marine waters of two antifouling compounds: Sodium hypochlorite and an alkylamine surfactant

Industrial wastes have a substantial impact on coastal environments. Therefore, to evaluate the impact of cooling water discharges from coastal power plants, we studied the kinetics of the degradative processes and the ecotoxicity of two antifouling products: (1) a classic antifouling product; sodium hypochlorite (NaClO) and (2) an alternative one; aliphatic amines (commercial under the registered trade mark Mexel^®432). To assess the persistence of both compounds the decay of sodium hypochlorite and the primary biodegradation rate of Mexel^®432 were determined in natural seawater at 20 °C. The results indicated a more rapid decay of NaClO than Mexel^®432. The degradation behavior of both chemicals was described following a logistic model, which permitted calculating kinetic parameters such as t₅₀ or t₉₀. The t₅₀ was 1 h and 2 d for NaClO and Mexel^®432, respectively. To evaluate the potential risks of the aforementioned treatments to marine organisms, the acute toxicity of both antifouling products was studied on the microalgae Isochrysis galbana and Dunaliella salina, and on the invertebrate Brachionus plicatilis, using growth inhibition and death tests as toxic response, respectively. For I. galbana, the 96-h EC₅₀ values were 2.91 ± 0.15 mg/L of NaClO and 4.55 ± 0.11 mg/L of Mexel^®432. D. salina showed values of 96-h EC₅₀ of 1.73 ± 0.16 mg/L of NaClO and 7.21 ± 0.1 mg/L of Mexel^®432. Brachionus plicatilis showed a 24-h LC₅₀ of 1.23 ± 0.1 mg/L of NaClO and 3.62 ± 0.37 mg/L of Mexel^®432. Acute toxicity was highly dependent on the chemical and species tested. NaClO presented more toxic effects than Mexel^®432, also B. plicatilis was the most sensitive species in both cases. The lowest NOECs obtained, 0.25 mg/L for NaClO and 2.12 mg/L for Mexel^®432, were similar to the theoretical residual concentrations of these biocides in cooling water discharges. Therefore, these discharges can cause undesirable negative effects upon the aquatic organisms present.     

Comparison of the microbiological and chemical characterization of harvested rainwater and reservoir water as alternative water resources

Rainwater harvesting (RWH) offers considerable potential as an alternative water supply. In this study, all of the harvested rainwater samples met the requirements for grey water but not for drinking water. In terms of microbiological parameters, total coliform (TC) and Escherichia coli (EC) were measured in 91.6% and 72%, respectively, of harvested rainwater samples at levels exceeding the guidelines for drinking water, consistent with rainfall events. In the case of the reservoir water samples, TC and EC were detected in 94.4% and 85.2%, respectively, of the samples at levels exceeding the guidelines for drinking water. Both indicators gradually increased in summer and fall. The highest median values of both TC and EC were detected during the fall. Chemical parameters such as common anions and major cations as well as metal ions in harvested rainwater were within the acceptable ranges for drinking water. By contrast, Al shows a notable increase to over 200 μg L^− 1 in the spring due to the intense periodic dust storms that can pass over the Gobi Desert in northern China. In terms of statistical analysis, the harvested rainwater quality showed that TC and EC exhibit high positive correlations with NO₃⁻ (ρ_TC = 0.786 and ρ_EC = 0.42) and PO₄⁻ (ρ_TC = 0.646 and ρ_EC = 0.653), which originally derive from catchment contamination, but strong negative correlations with Cl⁻ (ρ_TC = − 0.688 and ρ_EC = − 0.484) and Na⁺ (ρ_TC = − 0.469 and ρ_EC = − 0.418), which originate from seawater.     

The effects of phytophagous insects on water and soil nutrient concentrations and fluxes through forest stands of the Level II monitoring network in the UK

The effects of insect defoliators on throughfall and soil nutrient fluxes were studied in coniferous and deciduous stands at five UK intensive monitoring plots (1998 to 2008). Links were found between the dissolved organic carbon (DOC), nitrogen (N) and potassium (K) fluxes through the forest system to biological activity within the canopy. Underlying soil type determined the leaching or accumulation of these elements. Under oak, monitored at two sites, frass from caterpillars of Tortrix viridana and Operophtera brumata added direct deposition of ~ 16 kg ha⁻¹extra N during defoliation. Peaks of nitrate (NO₃-N) flux between 5 and 9 kg ha⁻¹ (×5 usual winter values) were recorded in consecutive years in shallow soil waters. Synchronous rises in deep soil NO₃-N fluxes at the Grizedale sandy site indicate downward flushing, not seen at the clay site. Under three Sitka spruce stands, generation of honeydew (DOC) was attributed to two aphid species (Elatobium abietinum and Cinara pilicornis) with distinctive feeding strategies. Throughfall DOC showed mean annual fluxes (6 seasons) ~ 45-60 kg ha⁻¹ compared with rainfall values of 14-22 kg ha⁻¹. Increases of total N in throughfall and NO₃-N fluxes in shallow soil solution were detected — soil water fluxes reached  8 kg ha⁻¹ in Llyn Brianne, ~ 25 kg ha⁻¹ in Tummel, and ~ 40 kg NO₃-N ha⁻¹ in Coalburn. At Tummel, on sandy soil, NO₃-N leaching showed increased concentration at depth, attributed to microbiological activity within the soil. By contrast, at Coalburn and Llyn Brianne, sites on peaty gleys, soil water NO₃-N was retained mostly within the humus layer. Soil type is thus key to predicting N movement and retention patterns. These long term analyses show important direct and indirect effects of phytophagous insects in forest ecosystems, on above and below ground processes affecting tree growth, soil condition, vegetation and water quality.     

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.     

Removal of Pharmaceutical and Personal Care Products (PPCPs) under nitrifying and denitrifying conditions

The contribution of volatilization, sorption and transformation to the removal of 16 Pharmaceutical and Personal Care Products (PPCPs) in two lab-scale conventional activated sludge reactors, working under nitrifying (aerobic) and denitrifying (anoxic) conditions for more than 1.5 years, have been assessed. Pseudo-first order biological degradation rate constants (k_biol) were calculated for the selected compounds in both reactors. Faster degradation kinetics were measured in the nitrifying reactor compared to the denitrifying system for the majority of PPCPs. Compounds could be classified according to their k_biol into very highly (k_biol > 5 L g_SS⁻¹ d⁻¹), highly (1 < k_biol < 5 L g_SS⁻¹ d⁻¹), moderately (0.5 < k_biol < 1 L g_SS⁻¹ d⁻¹) and hardly (k_biol < 0.5 L g_SS⁻¹ d⁻¹) biodegradable.Results indicated that fluoxetine (FLX), natural estrogens (E1 + E2) and musk fragrances (HHCB, AHTN and ADBI) were transformed to a large extent under aerobic (>75%) and anoxic (>65%) conditions, whereas naproxen (NPX), ethinylestradiol (EE2), roxithromycin (ROX) and erythromycin (ERY) were only significantly transformed in the aerobic reactor (>80%). The anti-depressant citalopram (CTL) was moderately biotransformed under both, aerobic and anoxic conditions (>60% and >40%, respectively). Some compounds, as carbamazepine (CBZ), diazepam (DZP), sulfamethoxazole (SMX) and trimethoprim (TMP), manifested high resistance to biological transformation.Solids Retention Time (SRT_aerobic >50 d and <50 d; SRT_anoxic >20 d and <20 d) had a slightly positive effect on the removal of FLX, NPX, CTL, EE2 and natural estrogens (increase in removal efficiencies <10%). Removal of diclofenac (DCF) in the aerobic reactor was positively affected by the development of nitrifying biomass and increased from 0% up to 74%. Similarly, efficient anoxic transformation of ibuprofen (75%) was observed after an adaptation period of 340 d. Temperature (16-26 °C) only had a slight effect on the removal of CTL which increased in 4%.     

Sediment reworking rates in deep sediments of the Mediterranean Sea

Different pelagic areas of the Mediterranean Sea have been investigated in order to quantify physical and biological mixing processes in deep sea sediments. Herein, results of eleven sediment cores sampled at different deep areas (> 2000 m) of the Western and Eastern Mediterranean Sea are presented.²¹⁰Pb_xs and ¹³⁷Cs vertical profiles, together with ¹⁴C dating, are used to identify the main processes characterising the different areas and, finally, controlling mixing depths (SML) and bioturbation coefficients (D_b). Radionuclide vertical profiles and inventories indicate that bioturbation processes are the dominant processes responsible for sediment reworking in deep sea environments.Results show significant differences in sediment mixing depths and bioturbation coefficients among areas of the Mediterranean Sea characterised by different trophic regimes. In particular, in the Oran Rise area, where the Almeria-Oran Front induces frequent phytoplankton blooms, we calculate the highest values of sediment mixing layers (13 cm) and bioturbation coefficients (0.187 cm² yr⁻¹), and the highest values of ²¹⁰Pb_xs and ¹³⁷Cs inventories. Intermediate values of SML and D_b (~ 6 cm and ~ 0.040 cm² yr⁻¹, respectively) characterise the mesothrophic Algero-Balearic basin, while in the Southern Tyrrhenian Sea mixing parameters (SML of 3 cm and D_b of 0.011 cm² yr⁻¹) are similar to those calculated for the oligotrophic Eastern Mediterranean (SML of 2 cm and D_b of ~ 0.005 cm² yr⁻¹).     

Nitritation performance and biofilm development of co- and counter-diffusion biofilm reactors: Modeling and experimental comparison

A comparative study was conducted on the start-up performance and biofilm development in two different biofilm reactors with aim of obtaining partial nitritation. The reactors were both operated under oxygen limited conditions, but differed in geometry. While substrates (O₂, NH₃) co-diffused in one geometry, they counter-diffused in the other. Mathematical simulations of these two geometries were implemented in two 1-D multispecies biofilm models using the AQUASIM software. Sensitivity analysis results showed that the oxygen mass transfer coefficient (K_i) and maximum specific growth rate of ammonia-oxidizing (AOB) and nitrite-oxidizing bacteria (NOB) were the determinant parameters in nitrogen conversion simulations. The modeling simulations demonstrated that K_i had stronger effects on nitrogen conversion at lower (0-10 m d⁻¹) than at the higher values (>10 m d⁻¹). The experimental results showed that the counter-diffusion biofilms developed faster and attained a larger maximum biofilm thickness than the co-diffusion biofilms. Under oxygen limited condition (DO < 0.1 mg L⁻¹) and high pH (8.0-8.3), nitrite accumulation was triggered more significantly in co-diffusion than counter-diffusion biofilms by increasing the applied ammonia loading from 0.21 to 0.78 g NH₄⁺-N L⁻¹ d⁻¹. The co- and counter-diffusion biofilms displayed very different spatial structures and population distributions after 120 days of operation. AOB were dominant throughout the biofilm depth in co-diffusion biofilms, while the counter-diffusion biofilms presented a stratified structure with an abundance of AOB and NOB at the base and putative heterotrophs at the surface of the biofilm, respectively.     

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.     

Investigating the potential role of ammonia in ion chemistry of fine particulate matter formation for an urban environment

To investigate the potential role of ammonia in ion chemistry of PM_2.5 aerosol, measurements of PM_2.5 (particulate matter having aerodynamic diameter < 2.5 µm) along with its ionic speciation and gaseous pollutants (sulfur dioxide (SO₂), nitrogen oxides (NO_x), ammonia (NH₃) and nitric acid (HNO₃)) were undertaken in two seasons (summer and winter) of 2007-2008 at four sampling sites in Kanpur, an urban-industrial city in the Ganga basin, India. Mean concentrations of water-soluble ions were observed in the following order (i) summer: SO₄²⁻ (26.3 µg m^− 3) > NO₃⁻ (16.8) > NH₄⁺ (15.1) > Ca²⁺ (4.1) > Na⁺ (2.4) > K⁺ (2.1 µg m^− 3) and (ii) winter: SO₄²⁻ (28.9 µg m^− 3) > NO₃⁻ (23.0) > NH₄⁺ (16.4) > Ca²⁺(3.4) > K⁺(3.3) > Na⁺ (3.2 µg m^− 3). The mean molar ratio of NH₄⁺ to SO₄²⁻ was 2.8 ± 0.6 (mostly >2), indicated abundance of NH₃ to neutralize H₂SO₄. The excess of NH₄⁺ was inferred to be associated with NO₃⁻ and Cl⁻. Higher sulfur conversion ratio (F_s: 58%) than nitrogen conversion ratio (F_n: 39%) indicated that SO₄²⁻ was the preferred secondary species to NO₃⁻. The charge balance for the ion chemistry of PM_2.5 revealed that compounds formed from ammonia as precursor are (NH₄)₂SO₄, NH₄NO₃ and NH₄Cl. This study conclusively established that while there are higher contributions of NH₄⁺, SO₄²⁻ to PM_2.5 in summer but for nitrates (in particulate phase), it is the winter season, which is critical because of low temperatures that drives the reaction between ammonia and HNO₃ in forward direction for enhanced nitrate formation. In summary, inorganic secondary aerosol formation accounted for 30% mass of PM_2.5 and any particulate control strategy should include optimal control of primary precursor gases including ammonia.     

Combined (alkaline + ultrasonic) pretreatment effect on sewage sludge disintegration

The individual effects of alkaline (pH 8-13) and ultrasonic (3750-45,000 kJ/kg TS) pretreatments on the disintegration of sewage sludge were separately tested, and then the effect of combining these two methods at different intensity levels was investigated using response surface methodology (RSM). In the combined pretreatment, ultrasonic treatment was applied to the alkali-pretreated sludge. While the solubilization (SCOD/TCOD) increase was limited to 50% in individual pretreatments, it reached 70% in combined pretreatment, and the results clearly showed that preconditioning of sludge at high pH levels played a crucial role in enhancing the disintegration efficiency of the subsequent ultrasonic pretreatment. By applying regression analysis, the disintegration degree (DD) was fitted based on the actual value to a second order polynomial equation: Y = −172.44 + 29.82X₁ + 5.30 × 10⁻³X₂ − 7.53 × 10⁻⁵X₁X₂ − 1.10X₁² − 1.043 × 10⁻⁷X₂², where X₁, X₂, and Y are pH, specific energy input (kJ/kg TS), and DD, respectively. In a 2D contour plot describing the tendency of DD with respect to pH and specific energy input, it was clear that DD increased as pH increased, but it seemed that DD decreased when the specific energy input exceeded about 20,000 kJ/kg TS. This phenomenon tells us that there exists a certain point where additional energy input is ineffective in achieving further disintegration. A synergetic disintegration effect was also found in the combined pretreatment, with lower specific energy input in ultrasonic pretreatment yielding higher synergetic effect. Finally, in order to see the combined pretreatment effect in continuous operation, the sludge pretreated with low intensity alkaline (pH 9)/ultrasonic (7500 kJ/kg TS) treatment was fed to a 3 L of anaerobic sequencing batch reactor after 70 days of control operation. CH₄ production yield significantly increased from 81.9 ± 4.5 mL CH₄/g COD_added to 127.3 ± 5.0 mL CH₄/g COD_added by pretreatment, and this enhanced performance was closely related to the solubilization increase of the sludge by pretreatment. However, enhanced anaerobic digestion resulted in 20% higher soluble N concentration in the reactor, which would be an additional burden in the subsequent nitrogen removal system.     

Nitrate and fluoride contamination in groundwater of an intensively managed agroecosystem: A functional relationship

A study was conducted to assess the potential of nitrate-nitrogen (NO₃-N) and fluoride (F) contamination in drinking groundwater as a function of lithology, soil characteristics and agricultural activities in an intensively cultivated district in India. Two hundred and fifty two groundwater samples were collected at different depths from various types of wells and analyzed for pH, electrical conductivity (EC), NO₃-N load and F content. Database on lithology, soil properties, predominant cropping systems, fertilizer and pesticide uses were also recorded for the district. The NO₃-N load in groundwater samples were low ranging from 0.12 to 6.58 μg mL^− 1 with only 8.7% of them contained greater than 3.0 μg mL^− 1 well below the 10 μg mL^− 1, the threshold limit fixed by WHO for drinking purpose. Samples from the habitational areas showed higher NO₃-N content over the agricultural fields. The content decreased with increasing depth of wells (r = − 0.25, P ≤ 0.01) and increased with increasing rate of nitrogenous fertilizer application (r = 0.90, P ≤ 0.01) and was higher in areas where shallow- rather than deep-rooted crops (r = − 0.28, P = ≤ 0.01, with average root depth) are grown. The NO₃-N load also decreased with increasing bulk density (r = − 0.73, P ≤ 0.01) and clay content (r = − 0.51, P ≤ 0.01) but increased with increasing hydraulic conductivity (r = 0.68, P ≤ 0.01), organic C (r = 0.78, P ≤ 0.01) and potential plant available N (r = 0.82, P ≤ 0.01) of soils. Fluoride content in groundwater was also low (0.02 to 1.15 μg mL^− 1) with only 4.0% of them exceeding 1.0 μg mL^− 1 posing a potential threat of fluorosis. On average, its content varied little spatially and along depth of sampling aquifers indicating little occurrence of F containing rocks/minerals in the geology of the district. The content showed a significant positive correlation (r = 0.234, P = ≤ 0.01) with the amount of phosphatic fertilizer (single super phosphate) used for agriculture. Results thus indicated that the groundwater of the study area is presently safe for drinking purpose but some anthropogenic activities associated with intensive cultivation had a positive influence on its loading with NO₃-N and F.     

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).     

Application of the Nernst-Planck approach to lead ion exchange in Ca-loaded Pelvetia canaliculata

Ca-loaded Pelvetia canaliculata biomass was used to remove Pb²⁺ in aqueous solution from batch and continuous systems. The physicochemical characterization of algae Pelvetia particles by potentiometric titration and FTIR analysis has shown a gel structure with two major binding groups - carboxylic (2.8 mmol g⁻¹) and hydroxyl (0.8 mmol g⁻¹), with an affinity constant distribution for hydrogen ions well described by a Quasi-Gaussian distribution. Equilibrium adsorption (pH 3 and 5) and desorption (eluents: HNO₃ and CaCl₂) experiments were performed, showing that the biosorption mechanism was attributed to ion exchange among calcium, lead and hydrogen ions with stoichiometry 1:1 (Ca:Pb) and 1:2 (Ca:H and Pb:H). The uptake capacity of lead ions decreased with pH, suggesting that there is a competition between H⁺ and Pb²⁺ for the same binding sites. A mass action law for the ternary mixture was able to predict the equilibrium data, with the selectivity constants α_Ca^H = 9 ± 1 and α_Ca^Pb = 44 ± 5, revealing a higher affinity of the biomass towards lead ions. Adsorption (initial solution pH 4.5 and 2.5) and desorption (0.3 M HNO₃) kinetics were performed in batch and continuous systems. A mass transfer model using the Nernst-Planck approximation for the ionic flux of each counter-ion was used for the prediction of the ions profiles in batch systems and packed bed columns. The intraparticle effective diffusion constants were determined as 3.73 × 10⁻⁷ cm² s⁻¹ for H⁺, 7.56 × 10⁻⁸ cm² s⁻¹ for Pb²⁺ and 6.37 × 10⁻⁸ cm² s⁻¹ for Ca²⁺.     

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.     

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.