Identification and quantitative detection of Legionella spp. in various aquatic environments by real-time PCR assay

In this study, a SYBR green quantitative real-time PCR was developed to quantify and detect the Legionella spp. in various environmental water samples. The water samples were taken from watershed, water treatment plant, and thermal spring area in Taiwan. Legionella was detected in 13.6 % (24/176), and the detection rate for river water, raw drinking water, and thermal spring water was 10, 21.4, and 16.6 %, respectively. Using real-time PCR, concentration of Legionella spp. in detected samples ranged between 9.75?×?10⁴ and 3.47?×?10⁵?cells/L in river water, 6.92?×?10⁴ and 4.29?×?10⁵?cells/L in raw drinking water, and 5.71?×?10⁴ and 2.12?×?10⁶?cells/L for thermal spring water samples. The identified species included Legionella pneumophila (20.8 %), Legionella jordanis (4.2 %), Legionella nautarum (4.2 %), Legionella sp. (4.2 %), and uncultured Legionella sp. (66.6 %). The presence of L. pneumophila in aquatic environments suggested a potential public health threat that must be further examined.     

Understanding the patterns and mechanisms of urban water ecosystem degradation: phytoplankton community structure and water quality in the Qinhuai River, Nanjing City, China

The temporal and spatial distribution characteristics of environmental parameters and the phytoplankton community were investigated in October 2010 and January 2011 in the Qinhuai River, Nanjing, China. Results showed that the water quality in the study area was generally poor, and the main parameters exceeding standards (level V) were nitrogen and phosphorus. The observed average concentrations of the total nitrogen (TN) were 4.90 mg?L^?1 in autumn and 9.29 mg?L^?1 in winter, and those of the total phosphorus (TP) were 0.24 mg?L^?1 in autumn and 0.88 mg?L^?1 in winter, respectively. Thirty-seven species, 30 genera, and four phyla of phytoplankton were detected in the river. Cyanophyta and Bacillariophyta were the dominant phyla in autumn, with average abundance and biomass of 221.5?×?10⁴?cells?L^?1 and 4.41 mg?L^?1, respectively. The dominant population in winter was Bacillariophyta, and the average abundance and biomass were 153.4?×?10⁴?cells?L^?1 and 6.58 mg?L^?1, respectively. The results of canonical correspondence analysis (CCA) between environmental parameters and phytoplankton communities showed that Chlorophyta could tolerate the higher concentrations of the permanganate index, nitrogen, and phosphorus in eutrophic water; Bacillariophyta could adapt well to changing water environments; and the TN/TP ratio had obvious impacts on the distributions of Cyanophyta, Euglenophyta, and some species of Chlorophyta. CCA analyses for autumn and winter data revealed that the main environmental parameters influencing phytoplankton distribution were water temperature, conductivity, and total nitrogen, and the secondary factors were dissolved oxygen, NH₄ ⁺–N, NO₃–N, TN, COD_Mn, TN/TP ratio, and oxidation-reduction potential.     

Is the microbiological quality of the Msunduzi River (KwaZulu-Natal, South Africa) suitable for domestic, recreational, and agricultural purposes?

As little is known about the potential risks associated with the use of microbiologically contaminated river water for recreation, irrigation, or domestic purposes, the Msunduzi River in Pietermaritzburg (KwaZulu-Natal, South Africa) was evaluated. In addition to pH, temperature, and chemical oxygen demand, quantitative and qualitative microbiological analyses were performed monthly for 13 months. These included aerobic plate counts, counts of aerobic and anaerobic sporeformers, most probable numbers for total and faecal coliforms and Escherichia coli and the detection of Salmonella spp., Staphylococcus aureus, and intestinal enterococci. Presumptive E. coli and S. aureus from river water samples were confirmed using PCR and additionally matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF MS) for E. coli. Aerobic plate counts were above the South African Department of Water Affairs recommended guideline level for domestic use of 100 cfu/ml for all 13 months assessed. Faecal coliform (up to 63,000 MPN/100 ml) and E. coli (up to 7,900 MPN/100 ml) levels regularly exceeded stipulated limits for safe irrigation, domestic and recreational use. The presence of Salmonella spp., S. aureus, and intestinal enterococci frequently coincided with faecal coliform and E. coli levels above 1,000 MPN/100 ml. This illustrates the value of using guideline values for faecal coliforms and E. coli as indicators for the presence of potential pathogens. PCR and MALDI-TOF MS confirmation of E. coli were in agreement, thereby demonstrating the potential of MALDI-TOF MS as a suitable alternative. These data demonstrate that potential health risks are associated with using Msunduzi River water for irrigation and recreational or domestic purposes.     

Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at ?0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10^?8 to 6.0 × 10^?8 mol L^?1 with detection and quantification limit 3.0 × 10^?9 and 1.0 × 10^?8 mol L^?1, respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.     

Use pattern of pesticides and their predicted mobility into shallow groundwater and surface water bodies of paddy lands in Mahaweli river basin in Sri Lanka

Pesticides applied on agricultural lands reach groundwater by leaching, and move to offsite water bodies by direct runoff, erosion and spray drift. Therefore, an assessment of the mobility of pesticides in water resources is important to safeguard such resources. Mobility of pesticides on agricultural lands of Mahaweli river basin in Sri Lanka has not been reported to date. In this context, the mobility potential of 32 pesticides on surface water and groundwater was assessed by widely used pesticide risk indicators, such as Attenuation Factor (AF) index and the Pesticide Impact Rating Index (PIRI) with some modifications. Four surface water bodies having greater than 20% land use of the catchment under agriculture, and shallow groundwater table at 3.0 m depth were selected for the risk assessment. According to AF, carbofuran, quinclorac and thiamethoxam are three most leachable pesticides having AF values 1.44 × 10^?2, 1.87 × 10^?3 and 5.70 × 10^?4, respectively. Using PIRI, offsite movement of pesticides by direct runoff was found to be greater than with the erosion of soil particles for the study area. Carbofuran and quinclorac are most mobile pesticides by direct runoff with runoff fractions of 0.01 and 0.08, respectively, at the studied area. Thiamethoxam and novaluron are the most mobile pesticides by erosion with erosion factions of 1.02 × 10^?4 and 1.05 × 10^?4, respectively. Expected pesticide residue levels in both surface and groundwater were predicted to remain below the USEPA health advisory levels, except for carbofuran, indicating that pesticide pollution is unlikely to exceed the available health guidelines in the Mahaweli river basin in Sri Lanka.     

Bioanalytical and instrumental analysis of estrogenic activities in drinking water sources from Yangtze River Delta

The estrogenic activities of source water from Yangtze River, Huaihe River, Taihu Lake and groundwater in Yangtze River Delta in the dry and wet season were determined by use of reporter gene assays based on African green monkey kidney (CV-1) cell lines. Higher estrogenic activities were observed in the dry season, and the estrogenic potentials in water samples from Taihu Lake were greater than other river basins. None of the samples from groundwater showed estrogen receptor (ER) agonist activity. The 17β-Estradiol (E2) equivalents (EEQs) of water samples in the dry season ranged from 9.41 × 10^?1 to 1.20 × 10¹ ng E2 L^?1. In the wet season, EEQs of all the water samples were below the detection limit as 9.00 × 10^?1 ng E2 L^?1 except for one sample from Huaihe River. The highest contribution of E2 was detected in Yangtze River as 99% of estrogenic activity. Nonylphenol (NP, 100% detection rate) and octylphenol (OP, 100% detection rate) might also be responsible for the estrogenic activities in water sources. Potential health risk induced by the estrogenic chemicals in source water may be posed to the residents through water drinking.     

Characterization of Cd-, Pb-, Zn-resistant endophytic Lasiodiplodia sp. MXSF31 from metal accumulating Portulaca oleracea and its potential in promoting the growth of rape in metal-contaminated soils

The aim of this study was to characterize the features of a Cd-, Pb-, and Zn-resistant endophytic fungus Lasiodiplodia sp. MXSF31 and to investigate the potential of MXSF31 to remove metals from contaminated water and soils. The endophytic fungus was isolated from the stem of Portulaca oleracea growing in metal-contaminated soils. The maximum biosorption capacities of MXSF31 were 3.0?×?10³, 1.1?×?10⁴, and 1.3?×?10⁴ mg kg^?1 for Cd, Pb, and Zn, respectively. The biosorption processes of Cd, Pb, and Zn by MXSF31 were well characterized with the pseudo-second-order kinetic model. The biosorption isotherm processes of Pb and Zn by the fungus were fitted better with the Langmuir model, while the biosorption processes of Cd was better fitted with the Freundlich model. The biosorption process of MXSF31 was attributed to the functional groups of hydroxyl, amino, carbonyl, and benzene ring on the cell wall. The active biomass of the strain removed more Cd, Pb, and Zn (4.6?×?10⁴, 5.6?×?10⁵, and 7.0?×?10⁴ mg kg^?1, respectively) than the dead biomass. The inoculation of MXSF31 increased the biomass of rape (Brassica napus L.), the translocation factor of Cd, and the extraction amount of Cd by rape in the Cd?+?Pb-contaminated soils. The results indicated that the endophytic fungus strain had the potential to remove heavy metals from water and soils contaminated by multiple heavy metals, and plants accumulating multiple metals might harbor diverse fungi suitable for bioremediation of contaminated media.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

Historical trend of nitrogen and phosphorus loads from the upper Yangtze River basin and their responses to the Three Gorges Dam

Excessive inputs of nitrogen and phosphorus (N and P) degrade surface water quality worldwide. Impoundment of reservoirs alters the N and P balance of a basin. In this study, riverine nutrient loads from the upper Yangtze River basin (YRB) at the Yichang station were estimated using Load Estimator (LOADEST). Long-term load trends and monthly variabilities during three sub-periods based on the construction phases of the Three Gorges Dam (TGD) were analyzed statistically. The dissolved inorganic nitrogen (DIN) loads from the upper YRB for the period from 1990 to 2009 ranged from 30.47?×?10⁴ to 78.14?×?10⁴ t, while the total phosphorus (TP) loads ranged from 2.54?×?10⁴ to 7.85?×?10⁴ t. DIN increased rapidly from 1995 to 2002 mainly as a result of increased fertilizer use. Statistics of fertilizer use in the upper YRB agreed on this point. However, the trend of the TP loads reflected the combined effect of removal by sedimentation in reservoirs and increased anthropogenic inputs. After the TGD impoundment in 2003, decreasing trends in both DIN and TP loads were found. The reduction in DIN was mainly caused by ammonium consumption and transference. From an analysis of monthly loads, it was found that DIN had a high correlation to discharges. For TP loads, an average decrease of 4.91 % in October was found when the TGD impoundment occurred, but an increase of 4.23 % also occurred in July, corresponding to the washout from sediment deposited in the reservoir before July. Results of this study revealed the TGD had affected nutrient loads in the basin, and it had played a role in nutrient reduction after its operation.     

Remediation of acid mine drainage (AMD)-contaminated soil by Phragmites australis and rhizosphere bacteria

Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10^?6 mol plant^?1 (Mn), 1.4?±?0.1?×?10^?3 mol plant^?1 (Fe), and 1.0?±?0.1?×?10^?4 mol plant^?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10^?6 mol plant^?1 (Mn), 3.5?±?0.06?×?10^?3 mol plant^?1 (Fe), and 5.0?±?0.2?×?10^?4 mol plant^?1 (Al) in soil added with 33.616 g C₆H₈O₇·H₂O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.     

In vitro assessment of corticosteroid effects of eight chiral herbicides

Abstract

Information regarding the enantioselective endocrine disruption of chiral herbicides is scarce. This study assessed the disrupting effects of eight typical chiral herbicides on corticosteroids (including glucocorticoids and mineralocorticoids). Enantioselectivity of eight chiral herbicides were evaluated for their agonistic/antagonistic effects on glucocorticoid receptor (GR) and mineralocorticoid receptor (MR) with CHOK1 cell line using reporter gene assay. Their influence on the production of corticosteroids were further investigated in H295R cell line using enzyme-linked immunosorbent assay (ELISA). None of the racemates or enantiomers of eight chiral herbicides exhibited GR or MR agonistic activity at non-cytotoxic concentrations. However, rac-propisochlor and S-imazamox antagonized cortisol-induced transactivation of GR by 21.79% and 38.73% at the concentration of 1.0?×?10^?7 M and 1.0?×?10^?6 M, respectively, and R-napropamide remarkably attenuated aldosterone-induced MR transactivation by 68.78% at 1.0?×?10^?6 M. The secretion of cortisol was significantly restrained after treated with 1.0?×?10^?6 M rac-propisochlor and rac-/R-napropamide at the concentration of 1.0?×?10^?6 M by 26.49%, 30.10% and 35.27%, respectively, while this glucocorticoid was remarkably induced by 1.0?×?10^?5 M rac-diclofop-methyl and its two enantiomers at the concentration of 1.0?×?10^?5 M by 75.60%, 100.1% and 68.78%, respectively. Exposure to rac-propisochlor (1.0?×?10^?6 M), S-diclofop-methyl (1.0?×?10^?5 M) or rac-/S-/R- acetochlor (1.0?×?10^?6 M) and rac-/S-/R-lactofen (1.0?×?10^?6 M) inhibited the secretion of aldosterone by approximately 40%. Our findings suggested that chiral herbicides disrupted corticosteroid homeostasis in an enantioselective way. Therefore, more comprehensive screening is required to better understand the ecological and health risks of chiral pesticides.     

Assessment of general condition of fish inhabiting a moderately contaminated aquatic environment

The assessment of general condition of fish in the moderately contaminated aquatic environment was performed on the European chub (Squalius cephalus) caught in September 2009 in the Sutla River in Croatia. Although increases of the contaminants in this river (trace and macro elements, bacteria), as well as physico-chemical changes (decreased oxygen saturation, increased conductivity), were still within the environmentally acceptable limits, their concurrent presence in the river water possibly could have induced stress in aquatic organisms. Several biometric parameters, metallothionein (MT), and total cytosolic protein concentrations in chub liver and gills were determined as indicators of chub condition. Microbiological and parasitological analyses were performed with the aim to evaluate chub predisposition for bacterial bioconcentration and parasitic infections. At upstream river sections with decreased oxygen saturation (～50 %), decreased Fulton condition indices were observed (FCI: 0.94 g?cm^?3), whereas gonadosomatic (GSI: 2.4 %), hepatosomatic (HSI: 1.31 %), and gill indices (1.3 %) were increased compared to oxygen rich downstream river sections (dissolved oxygen ～90 %; FCI: 1.02 g?cm^?3; GSI: 0.6 %; HIS: ～1.08 %; gill index: 1.0 %). Slight increase of MT concentrations in both organs at upstream (gills: 1.67 mg?g^?1; liver: 1.63 mg?g^?1) compared to downstream sites (gills: 1.56 mg?g^?1; liver: 1.23 mg?g^?1), could not be explained by induction caused by increased metal levels in the river water, but presumably by physiological changes caused by general stress due to low oxygen saturation. In addition, at the sampling site characterized by inorganic and fecal contamination, increased incidence of bacterial bioconcentration in internal organs (liver, spleen, kidney) was observed, as well as decrease of intestinal parasitic infections, which is a common finding for metal-contaminated waters. Based on our results, it could be concluded that even moderate contamination of river water by multiple contaminants could result in unfavourable living conditions and cause detectable stress for aquatic organisms.     

Neutral poly- and perfluoroalkyl substances in air and seawater of the North Sea

Concentrations of neutral poly- and perfluoroalkyl substances (PFASs), such as fluorotelomer alcohols (FTOHs), perfluoroalkane sulfonamides (FASAs), perfluoroalkane sufonamidoethanols (FASEs), and fluorotelomer acrylates (FTACs), have been simultaneously determined in surface seawater and the atmosphere of the North Sea. Seawater and air samples were taken aboard the German research vessel Heincke on the cruise 303 from 15 to 24 May 2009. The concentrations of FTOHs, FASAs, FASEs, and FTACs in the dissolved phase were 2.6–74, <0.1–19, <0.1–63, and <1.0–9.0 pg L^?1, respectively. The highest concentrations were determined in the estuary of the Weser and Elbe rivers and a decreasing concentration profile appeared with increasing distance from the coast toward the central part of the North Sea. Gaseous FTOHs, FASAs, FASEs, and FTACs were in the range of 36–126, 3.1–26, 3.7–19, and 0.8–5.6 pg m^?3, which were consistent with the concentrations determined in 2007 in the North Sea, and approximately five times lower than those reported for an urban area of Northern Germany. These results suggested continuous continental emissions of neutral PFASs followed by transport toward the marine environment. Air–seawater gas exchanges of neutral PFASs were estimated using fugacity ratios and the two-film resistance model based upon paired air–seawater concentrations and estimated Henry's law constant values. Volatilization dominated for all neutral PFASs in the North Sea. The air–seawater gas exchange fluxes were in the range of 2.5?×?10³–3.6?×?10⁵ pg m^?2 for FTOHs, 1.8?×?10²–1.0?×?10⁵ pg m^?2 for FASAs, 1.1?×?10²–3.0?×?10⁵ pg m^?2 for FASEs and 6.3?×?10²–2.0?×?10⁴ pg m^?2 for FTACs, respectively. These results suggest that the air–seawater gas exchange is an important process that intervenes in the transport and fate for neutral PFASs in the marine environment.     

Speciation and persistence of doxycycline in the aquatic environment: Characterization in terms of steady state kinetics

The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10^?2 and 4.5 × 10^?3 μgg^?1 day^?1) and sediment phase (7.9 × 10^?3 and 1.5 × 10^?3 μgg^?1 day^?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10^?3 μgg^?1 day^?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10^?3 μgg^?1 day^?1) and to microbial degradation (9.8 × 10^?3 μgg^?1 day^?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.     

Establishment of reference conditions for nutrients in an intensive agricultural watershed,Eastern China

Nutrient enrichment from nonpoint source pollution is one of the main causes of poor water quality and biotic impairment in many streams and rivers worldwide. The establishment of reference nutrient conditions in a river system is an essential but difficult task for water quality control. In the present study, the reference concentrations of total nitrogen (TN) and total phosphorus (TP) were estimated in an intensive agricultural watershed, the Cao-E River system of Eastern China. Based on a 3-year water quality monitoring data in the river system, three approaches were adopted to establish the reference concentrations of TN and TP, those are the 75th percentile of frequency distribution of nutrient concentrations in reference streams, the 25th percentile of frequency distribution of nutrient concentration in general streams (including reference and non-reference streams) and regression modeling. Results showed that the nutrient reference concentrations were slightly different from different approaches. By the three approaches, the average reference concentrations for TN and TP in the study system were 1.73?±?0.13 mg l^?1 and 55.23?±?4.77 μg l^?1 with CV of 7.39 % and 8.63 %, respectively. Accordingly, the reference concentrations for TN and TP were recommended to be 1.70 mg l^?1 and 55 μg l^?1, respectively. In the mountainous and intensive agricultural watershed, the major anthropogenic impacts to river water quality were the urban area percentage cover, cropland area with slopes 0–8°, and livestock and poultry waste loads density. These variables could account for 89.7 % and 80.3 % of the total variations for TN and TP concentration, respectively.     

Responses of kinetics and capacity of phenanthrene sorption on sediments to soil organic matter releasing

Soil organic matter (SOM) releasing with dissolved organic matter (DOM) formed in solution was confirmed in a sediment/water system, and the effects of SOM releasing on the sorption of phenanthrene on sediments were investigated. Inorganic salt (0–0.1 mol L^?1 NaCl) was used to adjust SOM releasing, and two sediments were prepared, the raw sediment (S1) from Weihe River, Shann’xi, China, and the eluted sediments with and without DOM supernatant remained, termed as S2a and S2b, respectively. The FTIR and ¹H NMR analysis indicate that the low molecular weight hydrophilic SOM fraction released prior to the high molecular weight hydrophobic fraction. As a response, phenanthrene sorption kinetics on S1 showed atypical and expressed as three stages: rapid sorption, pseudo sorption with partial desorption, and slow sorption, thus a defined “sorption valley” occurred in kinetic curve. In all cases, partition dominates the sorption, and sorption capacity (K_d) ranked as S2b > S1 > S2a. Compared with the alterations of sediment characters, DOM solubilization produced by SOM releasing exhibited a greater inhibitory effect on sorption with a relative contribution of 0.67. Distribution coefficients (K_doc) of PHE into DOM clusters were 2.10?×?10⁴–4.18?×?10⁴ L kg^?1, however a threshold concentration of 6.83 mg L^?1 existed in DOM solubilization. The study results will help to clarify PAHs transport and their biological fate in a sediment/water system.     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

Input-export fluxes of heavy metals in the Cochin estuary,southwest coast of India

Cochin estuary (CE) is one of the largest tropical estuaries along the southwest coast of India, sustaining rich bio-resources. Several studies enlighten the environmental changes in the CE caused by anthropogenic activities. In the present study, an attempt has been made to quantify the heavy metal (dissolved and particulate) fluxes brought by the six rivers into the CE with their exchange into the coastal ocean through the major inlet at Cochin during a steady flow period (October–November 2015). The water flux across the inlet was quantified using an acoustic doppler current profiler. The measured daily input of dissolved metals from the rivers was 2.43?×?10³ kg Fe, 334 kg Zn, 259 kg Ni, and 83 kg Cr, while that of particulate metals were 85.30?×?10³ kg Fe, 8. 6?×?10³ kg Mn, 236.9 kg Cr, and 111.9 kg Zn. The net export of metals through the Cochin inlet (per tidal cycle) was 3.3?×?10³ kg Fe, 515 kg Cr, 150 kg Zn, and 5 kg Ni in dissolved form and 3.32?×?10⁵ kg Fe, 1747 kg Mn, 1636 kg Cr, 1397 kg Zn, and 586 kg Ni in particulate form. The high concentrations of metals during ebb tides are clear indications of their contribution from the industrial conglomerates (industrial units of metallurgy, catalyst, fertilizer, and pesticides) located in the Periyar River. The significance of this study is that the export fluxes may increase further during the summer monsoon (June to September), which may impact the abundant fishery emanating in the coastal environment during the period due to intense upwelling.

     

Selective sensing of mercury(II) using PVC-based membranes incorporating recently synthesized 1,3-alternate thiacalix[4]crown ionophore

The construction and electrodes characteristics of poly(vinylchloride) (PVC)-based polymeric membrane electrode (PME) and coated graphite electrode (CGE), incorporating 1,3-alternate thiacalix[4]crown as ionophore for estimation of Hg(II) ions, are reported here. The best potential response was observed for PME-1 having membrane composition of: ionophore (6.2 mg), PVC (100.0 mg), 2-nitrophenyl octyl ether (2-NPOE; 200.0 mg), and sodium tetraphenyl borate (NaTPB; 2.0 mg); for CGE-1 with the membrane composition: ionophore (3.5 mg), PVC (40.0 mg), 2-NPOE (80.0 mg), and NaTPB (2.0 mg). The electrodes exhibits Nernstian slope of 29.16 mV/decade with PME-1 and 30.39 mV/decade with CGE-1 for Hg(II) ions over wide concentration range, i.e., 1.0?×?10^?1 to 5.0?×?10^?6?M with PME-1 and 1.0?×?10^?1 to 5.0?×?10^?7?M with CGE-1. Lower detection limits were found to be 9.77?×?10^?6?M for PME-1 and 7.76?×?10^?7?M for CGE-1 with response time varying from 10 to 20 s. Also, these electrodes work within pH range of 2.0–6.0 for PME-1 and 1.5–6.5 for CGE-1. Overall, CGE-1 has been found to be better than PME-1. CGE-1 has been used as indicator electrode for the potentiometric titration of Hg(II) ions with EDTA as well as successfully applied for determination of Hg(II) content in wastewater, insecticide, dental amalgam, and ayurvedic medicines samples with very good performance (0.9974 correlation coefficient in the comparison against volumetric method).     

Role of some organic inhibitors on the oxidation of dissolved sulfur dioxide by oxygen in rainwater medium

In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R _o = k _o[S(IV)]], where k _o is the first-order rate constant and R _o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k _obs = k _o/(1 + B [Inh]), where k _obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10^?5 to 1.5?×?10^?4 s^?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?10⁴) (ethanol) and (3.95?±?2.36)?×?10⁴ (2-butanol) at 25 °C.