Occurrence of alternative flame retardants in indoor dust from New Zealand: indoor sources and human exposure assessment

Due to worldwide restrictions on polybrominated diphenyl ethers (PBDEs), the demand for alternative flame retardants (AFRs), such as organophosphate flame retardants (OPFRs), novel brominated FRs (NBFRs) and hexabromocyclododecanes (HBCDs), has recently increased. Little is known about human exposure to NBFRs and OPFRs and that their levels in dust have been scarcely evaluated worldwide. To increase the knowledge regarding these chemicals, we measured concentrations of five major NBFRs, ten OPFRs and three HBCD isomers in indoor dust from New Zealand homes. Dust samples were taken from living room floors (n=34) and from mattresses of the same houses (n=16). Concentrations (ngg(-1)) of NBFRs were: 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (<2-175), decabromodiphenyl ethane (DBDPE) (<5-1430), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (<2-2285) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (<2-640). For OPFRs, concentrations (ngg(-1)) ranged between: tri-ethyl-phosphate (TEP) (<10-235), tri-n-butyl-phosphate (TnBP) (<20-7545), tris-(2-chloroethyl)-phosphate (TCEP) (<20-7605), tris-(1-chloro-2-propyl) phosphate (TCPP) (20-7615), tri-(2-butoxyethyl)-phosphate (TBEP) (50-27325), tris-(2,3-dichloropropyl)-phosphate (TDCPP) (20-16560), tri-phenyl-phosphate (TPhP) (20-35190), and tri-cresyl-phosphate (TCP) (<50-3760). HBCD concentrations fell in the range <2-4100ngg(-1). BTBPE, DBDPE, TBPH, TBEP, and TnBP showed significant positive correlation (p<0.05) between their concentrations in mattresses and the corresponding floor dust (n=16). These data were used to derive a range of plausible exposure scenarios. Although the estimated exposure is well below the corresponding reference doses (RfDs), caution is needed given the likely future increase in use of these FRs and the currently unknown contribution to human exposure by other pathways such as inhalation and diet.     

Electrocatalytic reduction of nitrate ions from water using polyaniline nanofibers modified gold electrode

Polyaniline (PANI) nanofibers were electrochemically synthesized on gold electrode using ethanol as soft template by the cyclic voltammetry technique. The PANI nanofibers were characterized by Fourier transform infrared spectroscopy, UV-visible spectroscopy, and scanning electron microscopy. Linear sweep voltammetry was used to investigate electrocatalytic activity of the PANI nanofibers modified electrode toward the reduction of nitrate ions. Results showed that the electroreduction process strongly depends on the applied potential. At the potential value of about -0.8 V vs Ag/AgCl, the electroreduction of nitrate anions to nitrite anions was identified as the rate-determining step of the electroreduction process. In the potential range of -0.8 to -1.0 V, reduction of nitrite to hydroxylamine occurs, followed by the reduction to ammonia. At potentials more negative than -1.0 V, nitrite is directly reduced to ammonia. This study demonstrates the effectiveness of PANI nanofibers modified electrode in the electroreduction of nitrate ions compared to traditional reduction methods.     

Chromium removal from water by activated carbon developed from waste rubber tires

Because of the continuous production of large amount of waste tires, the disposal of waste tires represents a major environmental issue throughout the world. This paper reports the utilization of waste tires (hard-to-dispose waste) as a precursor in the production of activated carbons (pollution-cleaning adsorbent). In the preparation of activated carbon (AC), waste rubber tire (WRT) was thermally treated and activated. The tire-derived activated carbon was characterized by means of scanning electron microscope, energy-dispersive X-ray spectroscopy, FTIR spectrophotometer, and X-ray diffraction. In the IR spectrum, a number of bands centred at about 3409, 2350, 1710, 1650, and 1300–1000 cm^?1 prove the present of hydroxyl and carboxyl groups on the surface of AC in addition to C═C double bonds. The developed AC was tested and evaluated as potential adsorbent removal of chromium (III). Experimental parameters, such as contact time, initial concentration, adsorbent dosage and pH were optimized. A rapid uptake of chromium ions was observed and the equilibrium is achieved in 1 h. It was also found that the adsorption process is pH dependent. This work adds to the global discussion of the cost-effective utilization of waste rubber tires for waste water treatment.     

Kinetic behavior of anti-inflammatory drug ibuprofen in aqueous medium during its degradation by electrochemical advanced oxidation

The electrochemical abatement of the drug ibuprofen (2-(4-isobutylphenyl)propionic acid) from aqueous solution has been carried out by anodic oxidation. The electrolyses have been performed at constant current using a small, undivided cell equipped with a Pt or thin-film boron-doped diamond (BDD) anode and a carbon-felt cathode. The results have shown that ibuprofen has been destroyed under all the conditions tested, following pseudo-first-order kinetics; however, BDD enables higher removal rates than Pt, because the former produces greater quantity of ^?OH. Using BDD anode, the pseudo-first-order rate constant increased with applied current and when NaCl replaced Na₂SO₄ as supporting electrolyte, while it is almost unaffected by ibuprofen concentration. Mineralization of ibuprofen aqueous solutions was followed by total organic carbon (TOC) measurements. After 8 h of electrolysis, TOC removal varied from 91 % to 96 % applying a current in the range of 50–500 mA. The reaction by-products were quantified by chromatographic techniques, and in particular, aliphatic acids (oxalic, glyoxylic, formic, acetic, and pyruvic) have been the main intermediates formed during the electrolyses. The absolute rate constant for the oxidative degradation of ibuprofen have also been determined, by competition kinetic method, as 6.41?×?10⁹ M^?1?s^?1.     

Thermodynamic and kinetic studies of As(V) removal from water by zirconium oxide-coated marine sand

Arsenic contamination of groundwater is a major threat to human beings globally. Among various methods available for arsenic removal, adsorption is fast, inexpensive, selective, accurate, reproducible and eco-friendly in nature. The present paper describes removal of arsenate from water on zirconium oxide-coated sand (novel adsorbent). In the present work, zirconium oxide-coated sand was prepared and characterised by infrared and X-ray diffraction techniques. Batch experiments were performed to optimise different adsorption parameters such as initial arsenate concentration (100–1,000 μg/L), dose (1–8 g/L), pH of the solution (2–14), contact time (15–150 min.), and temperature (20, 30, 35 and 40 °C). The experimental data were analysed by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. Furthermore, thermodynamic and kinetic parameters were evaluated to know the mode of adsorption between ZrOCMS and As(V). The maximum removal of arsenic, 97 %, was achieved at initial arsenic concentration of 200 μg/L, after 75 min at dosage of 5.0 g/L, pH?7.0 and 27?±?2 °C. For 600 μg/L concentration, the maximum Langmuir monolayer adsorption capacity was found to be 270 μg/g at 35 °C. Kinetic modelling data indicated that adsorption process followed pseudo-second-order kinetics. The mechanism is controlled by liquid film diffusion model. Thermodynamic parameter, ΔH°, was ?57.782, while the values of ΔG° were ?9.460, ?12.183, ?13.343 and ?13.905 kJ/mol at 20, 30, 35 and 40 °C, respectively, suggesting exothermic and spontaneous nature of the process. The change in entropy, ΔS°?=??0.23 kJ/mol indicated that the entropy decreased due to adsorption of arsenate ion onto the solid adsorbent. The results indicated that the reported zirconium oxide-coated marine sand (ZrOCMS) was good adsorbent with 97 % removal capacity at 200 μg/L concentration. It is interesting to note that the permissible limit of arsenic as per World Health Organization is 10 μg/L, and in real situation, this low concentration can be achieved through this adsorbent. Besides, the adsorption capacity showed that this adsorbent may be used for the removal of arsenic from any natural water resource.     

Environmental monitoring of complex hydrocarbon mixtures in water and soil samples after solid phase microextraction using PVC/MWCNTs nanocomposite fiber

A novel nanocomposite based on incorporation of multiwalled carbon nanotubes (MWCNTs) in polyvinyl chloride (PVC) was prepared. Proposed nanocomposite was coated on stainless steel wire by deep coating. Composition of nanocomposite was optimized based on results of morphological studies using scanning electron microscopy. The best composition (83% MWCNTs:17% PVC) was applied as a solid phase microextraction fiber. Complex mixture of aromatic (BTEX) and aliphatic hydrocarbons (C₅–C₃₄) were selected as model analytes, and performance of proposed fiber in extraction of the studied compounds from water and soil samples was evaluated. Analytical merits of the method for water samples (LODs = 0.10–1.10 ng L⁻¹, r² = 0.9940–0.9994) and for soil samples (LODs = 0.10–0.77 ng kg⁻¹, r² = 0.9946–0.9994) showed excellent characteristics of it in ultra trace determination of petroleum type environmental pollutants. Finally, the method was used for determination of target analytes in river water, industrial effluent and soil samples.     

Are deep eutectic solvents benign or toxic?

In continuation of investigation for environmentally benign protocol for new solvents termed deep eutectic solvents (DESs), it is herein reported results concerning the toxicity and cytotoxicity of choline chloride (ChCl) based DESs with four hydrogen bond donors including glycerine, ethylene glycol, triethylene glycol and urea. The toxicity was investigated using two Gram positive bacteria Bacillus subtilis and Staphylococcus aureus, and two Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The cytotoxicity effect was tested using the Artemia salina leach. It was found that there was no toxic effect for the tested DESs on all of the studied bacteria confirming their benign effects on these bacteria. Nevertheless, it was found that the cytotoxicity of DESs was much higher than their individual components (e.g. glycerine, ChCl) indicating that their toxicological behavior is different. For our best knowledge this is the first time that toxicity and cytotoxicity of DESs were studied. The toxicity and cytotoxicity of DESs varied depending on the structure of components. Careful usage of the terms non-toxicity and biodegradability must be considered. More investigation on this matter is required.     

Ecological impacts of the N-viro biosolids land-application for wild blueberry (Vaccinium angustifolium. Ait) production in Nova Scotia

Land application of biosolids from processed sewage sludge may deteriorate soil, water, and plants. We investigated the impact of the N-Viro biosolids land-application on the quality of the soil water that moved through Orthic Humo-Ferric Podzols soil of Nova Scotia (NS) at the Wild Blueberry Research Institute, Debert, NS Canada. In addition, the response of major soilproperties and crop yield was also studied. Wild blueberry (Vaccinium angustifolium. Ait) was grown under irrigated and rainfed conditions in 2008 and 2009. Four experimental treatments including (i) NI: N-Viro irrigated, (ii) NR: N-Viro rainfed, (iii) FI: inorganic fertilizer irrigated, and (iv) FR: inorganic fertilizer rainfed (control) were replicated 4 times under randomized complete block design. Soil samples were collected at the end of each year and analyzed for changes in cation exchange capacity (CEC), soil organic matter (SOM), and pH.Soil water samples were collected four times during the study period from the suction cup lysimeters installed within and below crop root zone at 20 and 40 cm depths, respectively. The samples were analyzed for a range of water quality parameters including conductance, hardness, pH, macro- and micronutrients, and the infectious pathogens Escherichia coli (E. coli) and salmonella. Berries were harvested for fruit yield estimates. Irrigation significantly increased CEC during 2008 and the soil pH decreased from 4.93 (2008) to 4.79 (2009). There were significant influences of irrigation, fertilizer, and their interaction, in some cases, on most of the soil water quality parameters except on the infectious bacteria. No presence of E. coli or salmonella were observed in soil and water samples, reflecting the absence of these bacteria in biosolids used in this experiment. Nutrient concentration in the soil water samples collected from the four treatments were higher in the sequence NI > NR > FI > FR. The irrigation treatment had significant effect on the unripe fruit yield. We conclude that the comparable performance of N-Viro biosolids and the increasing prices of inorganic fertilizers would compel farmers to use economically available N-Viro biosolids that, coupled with the supplemental irrigation, did not deteriorate the studied soil properties, soil water quality, and the wild blueberry yield during this experiment.     

Land-use change and its socio-environmental impact in Eastern Ethiopia’s highland

The Alemaya district (Eastern Ethiopian highlands) is characterized by undulating physiographic features with arid, semi-arid, and humid climatic conditions. This study evaluated socio-environmental changes in land use and land cover during 1985–2011. Screen digitization on remotely sensed data (i.e., Landsat images from 1985 to 2011) was performed to produce 10 classes of land use and land cover. Then, final land-use maps were prepared using a geographic information system following field verification and accuracy assessment. The drying of water bodies, including the prominent lakes Alemaya, Adele, and Tinike, had been the most important environmental change observed. Degraded land, marsh, perennial cropland, and residential areas increased by 37, 438, 42, and 190 %, respectively, whereas grassland, plantation, shrubland, and temporal cropland decreased by 64, 11, 63, and 29 %, respectively. The increase in land degradation (+37 %), the other major observed problem, has made large areas unsuitable for agriculture and has reduced crop productivity. These land-use and land-cover changes have affected both the environment and the livelihoods of local residents; especially the issue related to land degradation requires urgent attention.     

Adverse effects in wild fish living downstream from pharmaceutical manufacture discharges

A set of biochemical and histological responses was measured in wild gudgeon collected upstream and downstream of urban and pharmaceutical manufacture effluents. These individual end-points were associated to fish assemblage characterisation. Responses of biotransformation enzymes, neurotoxicity and endocrine disruption biomarkers revealed contamination of investigated stream by a mixture of pollutants. Fish from sampled sites downstream of the industrial effluent exhibited also strong signs of endocrine disruption including vitellogenin induction, intersex and male-biased sex-ratio. These individual effects were associated to a decrease of density and a lack of sensitive fish species. This evidence supports the hypothesis that pharmaceutical compounds discharged in stream are involved in recorded endocrine disruption effects and fish population disturbances and threaten disappearance of resident fish species. Overall, this study gives argument for the utilisation of an effect-based monitoring approach to assess impacts of pharmaceutical manufacture discharges on wild fish populations.