Vapor-phase concentrations of PAHs and their derivatives determined in a large city: Correlations with their atmospheric aerosol concentrations

Thirteen PAHs, five nitro-PAHs and two hydroxy-PAHs were determined in 55 vapor-phase samples collected in a suburban area of a large city (Madrid, Spain), from January 2008 to February 2009. The data obtained revealed correlations between the concentrations of these compounds and a series of meteorological factors (e.g., temperature, atmospheric pressure) and physical–chemical factors (e.g., nitrogen and sulfur oxides). As a consequence, seasonal trends were observed in the atmospheric pollutants. A “mean sample” for the 14-month period would contain a total PAH concentration of 13 835 ± 1625 pg m⁻³ and 122 ± 17 pg m⁻³ of nitro-PAHs. When the data were stratified by season, it emerged that a representative sample of the coldest months would contain 18 900 ± 2140 pg m⁻³ of PAHs and 150 ± 97 pg m⁻³ of nitro-PAHs, while in an average sample collected in the warmest months, these values drop to 9293 ± 1178 pg m⁻³ for the PAHs and to 97 ± 13 pg m⁻³ for the nitro-PAHs. Total vapor phase concentrations of PAHs were one order of magnitude higher than concentrations detected in atmospheric aerosol samples collected on the same dates. Total nitro-PAH concentrations were comparable to their aerosol concentrations whereas vapor phase OH-PAHs were below their limits of the detection, indicating these were trapped in airborne particles.     

Ecotoxicity and fungal deterioration of recycled polypropylene/wood composites: Effect of wood content and coupling

Recycled polypropylene (rPP) was recovered from an industrial shredder and composites were prepared with a relatively wide range of wood content and with two coupling agents, a maleated PP (MAPP) and a maleated ethylene-propylene-diene elastomer (MAEPDM). The mechanical properties of the composites showed that the coupling agents change structure only slightly, but interfacial adhesion quite drastically. The durability of the materials was determined by exposing them to a range of fungi and, ecotoxicity was studied on the aquatic organism Vibrio fischeri. The composites generally exhibit low acute toxicity, with values below the levels considered to have direct ecotoxic effect on aquatic ecosystems (<2 toxic units). Their toxicity to V. fischeri depended on the presence of the coupling agents with larger E₅₀ values in 24-h aqueous extracts from composites containing MAPP or MAEPDM in comparison to composites without any coupling agent. Evaluation of resistance against fungal colonization and deterioration proved that wood facilitates fungal colonization. Fungi caused slight mass loss (below 3%) but it was not correlated with substantial deterioration in material properties. MAPP seems to be beneficial in the retention of mechanical properties during fungal attack. rPP/wood composites can be considered non-ecotoxic and quite durable, but the influence of wood content on resistance to fungal attack must be taken into account for materials intended for applications requiring long-term outdoor exposure.     

Ni/Fe-supported over hydrotalcites precursors as catalysts for clean and selective oxidation of Basic Yellow 11: Reaction intermediates determination

In this work, Basic Yellow 11 (BY 11) was employed as model compound to study catalytic wet air oxidation as a pre-treatment step to the conventional biological oxidation. Ni and Fe catalysts supported over hydrotalcite (HT) were prepared by incipient wetness and excess impregnation to obtain catalysts with different metal loadings (from 1 to 10 wt.%). HTs were synthesized by co-precipitation and characterized with XRD, X-ray fluorescence (XRF), BET, thermogravimetric analysis and SEM. Results showed that dye conversion increased with Ni and Fe content up to 7 wt.% and that the most effective catalyst were prepared by incipient wetness impregnation. The influence of metal loading in the catalyst, and the preparation method as well as the reaction conditions was investigated. A mechanism and reaction pathways for BY 11 during catalytic liquid phase oxidation have also been proposed.     

Combined phytoremediation of metal-working fluids with maize plants inoculated with different microorganisms and toxicity assessment of the phytoremediated waste

The aim of this study was to validate the effectiveness of a phytoremediation procedure for metal-working fluids (MWFs) with maize plants growing in hydroponic culture in which the roots grow on esparto fibre and further improve bioremediation potential of the system with root beneficial bacteria, seeking a synergistic effect of the plant–microorganism combination. Chemical oxygen demand (COD), pH, total and type of hydrocarbons measured after phytoremediation indicated that the process with maize plants was successful, as demonstrated by the significant decrease in the parameters measured. This effect was mainly due to the plant although inoculated microorganisms had a relevant effect on the type of remaining hydrocarbons. The success of the phytoremediation process was further confirmed by two toxicity tests, one of them based on chlorophyll fluorescence measurements on maize plants and another one based on cyanobacteria, using a bioluminescent toxicity bioassay; both tests demonstrated that the phytoremediated waste was significantly less toxic than the initial non-phytoremediated MWFs.     

Monitoring of pesticide residues in a cotton crop soil

Abstract

This paper reports on the residues of methyl parathion (O,O‐dimethyl O‐4‐nitrophenyl phosphorothioate), trifluralin (α, α, α‐trifluoro‐2, 6‐dinitro‐N, N‐dipropyl‐p‐toluidine), endosulfan [(1, 4, 5, 6, 7, 7‐hexachloro‐8, 9, 10‐trinorborn‐5‐en‐2, 3‐ylenebismethylene) sulfite] and dimethoate (O, O‐dimethyl S‐methylcarbamoylmethyl phosphorodithioate) in a cotton crop soil. Soil samples (0–15 cm) were collected at different periods from the cotton crop farm and subjected to Soxhlet extraction. The extracted material was analysed after clean‐up by a HP5890 II gas Chromatograph equipped with a ⁶³Ni electron‐capture detector (ECD‐⁶³Ni) and fitted with a 25m x 0,2mm i.d. fused silica capillary column [Ultra‐2 (5% phenylmethyl polysiloxane)]. The recoveries of the pesticide residues from the spiked control soil were determined after Soxhlet extraction and C₁₈ cartridges clean‐up by using radiotracer techniques with the corresponding ¹⁴C‐pesticides. The results show that in the cotton crop soil the pesticide residues under study were present in the range of 0.1 to 0.4 mg ? kg^‐1. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'_W) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb_T) in pure water. Experimental breakthrough volumes (Vb_E) were first determined using purified and deionized water as the matrix for selected compounds having Vb_T < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4–5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb_E curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5–6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb_E in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

Adsorption of chloridazon from aqueous solution on modified kerolite-rich materials

The adsorption of chloridazon (5-amine-4-chloro-2-phenylpyridazin-3(2H)-one) on kerolite samples heated at 110°C (K-110), 200°C (K-200), 400°C (K-400), 600°C (K-600) and acid-treated with H₂SO₄ solutions of two different concentrations (0.25 and 0.5 M) (K-0.25 and K-0.5, respectively) from pure water at 25°C has been studied by using batch and column experiments. The adsorption experimental data points were fitted to the Freundlich equation in order to calculate the adsorption capacities (K_f) of the samples; K_f values ranged from 184.7 mg kg^?1 (K-0.5) up to 2253 mg kg^?1 (K-600). This indicated that the heat treatment given to the kerolite greatly increases its adsorption capacity for the herbicide whereas the acid treatment produces a clear decrease in the amount of chloridazon adsorbed. The removal efficiency (R) was also calculated; R values ranging from 52.8% (K-0.5) up to 88.3% (K-600). Thus, the results showed that the 600°C heat-treated kerolite was more effective in relation to adsorption of chloridazon and it might be reasonably used in removing this herbicide from water.     

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics,reaction intermediates,and toxicity assessment

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄ of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺ and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄ ⁺, NO₃ ^?, and SO₄ ^2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.     

Designing conservation-development policies for the forest frontier

The conservation of forests in expanding frontier landscapes is critically important to maintain intact forest ecosystems and support forest dependent communities. To conserve frontier forests, policy approaches are needed that conserve forests and advance the well-being of local resource dependent communities. To identify such approaches, the forest conservation and development framework (FCDF) was designed to find place-based conservation-development policies that target system leverage-points influencing land-use practices. To demonstrate the utility of the FCDF, a portfolio of conservation-development policies were identified for Peru’s Manu-Tambopata Corridor (MAT) and evaluated by local land-users. Results of the MAT case study show high levels of interest in the proposed policies, but a wide variation in interest levels relative to personal circumstances and policies proposed. Barriers to implementing conservation-development policies in frontier environments were also identified, including high value land-use alternatives generating high opportunity costs for accepting PES payments (e.g., REDD+), insecure land tenure and conflicting authorizations limiting land-users policy choices, and broad demographic diversity among local land-users. Collectively, this research suggests the FCDF is a useful approach for identifying policies matched to local conditions that advance conservation and human development. This research also indicates policy design in frontier environments is most effective when adapted to local conditions, seeks to identify a mix of complementary policies, and is targeted at key system variables influencing land-use practices (i.e., system leverage-points). Importantly, the MAT case study also highlights how even in rapidly changing frontier landscapes, land-users are interested in policies that advance conservation and development goals.     

Kinetic effects on the interactions of Rh(III) with humic acids as determined using size-exclusion chromatography (SEC)

The anthropogenic inputs of Rh in the environment—together with other platinum group elements—have increased considerably during the last 20–30 years. However, thermodynamics and kinetics on the interaction of Rh with natural organic and inorganic ligands are still poorly characterized. Here, we report the time-dependent speciation of rhodium chlorides spiked to model freshwater with and without the presence of humic substances. Rhodium species were determined using size-exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS). Results indicate that organic matter can effectively bind rhodium, but the extremely slow reaction kinetics of Rh plays a significant role on its speciation in natural waters. Accordingly, formation of Rh-organic complexes from spiked rhodium chlorides required around 15 days to reach equilibrium; this should be taken into account in those laboratory experiments where the biological interactions of Rh, using spiked samples, are studied. Regarding Rh inorganic speciation in freshwater, the available thermodynamic constants predict the dominance of the neutral trihydroxo and negatively charged tetrahydroxo rhodium complexes over typical pHs (6–8); our results, however, indicate only the presence of negatively charged hydroxocomplexes at pH 7. Reexamination of the Rh stability constants suggest that these hydroxylated rhodium complexes may also dominate its inorganic speciation in seawater.