In this study, we have reported the synthesis of new amino-substituted p-tert-butylcalix[4]arene (3) and its application for the removal of two carcinogenic azo dyes, i.e., Chicago Sky Blue (CSB) and Tropaeolin 000 (TP) from aqueous environment. The newly synthesized calix–ligand 3 is characterized by FT-IR and ¹H NMR spectroscopy as well as elemental analysis. The extraction efficiency of newly calix–ligand 3 for CSB and TP dyes from aqueous media was evaluated through liquid–liquid extraction experiments. The newly synthesized calix–ligand 3 showed outstanding extraction percentage and maximum percent extraction, i.e., 97 and 96 % of CSB and TP dyes was achieved at pH 9, respectively. During the extraction process, effect of various parameters was monitored and found that extraction is highly dependent on pH and salinity. Moreover, cyclic structure, cavity size, functional groups of the calixarene derivative, hydrophobicity, and the ionic property of guest molecules also affect the extraction efficiency. The comparative data prop up calix–ligand 3 as an effective extractant for both CSB and TP dyes.

A novel porous biomorph-genetic composite of α-Fe₂O₃/Fe₃O₄/C (PBGC-Fe/C) with eucalyptus wood template was prepared, characterized and tested for its sorption capacity of As(V) from aqueous solution. The result indicated that the PBGC-Fe/C material retained the hierarchical porous structure of eucalyptus wood with three different types of pores (widths 70∼120, 4.1∼6.4 and 0.1∼1.3 μm) originating from vessels, fibres and pits of the wood, respectively. Its surface area was measured to be 59.2 m²/g. With increasing initial As(V) concentration from 5 to 100 mg/L, the amounts of As(V) sorbed on the pulverized PBGC-Fe/C sorbent (<0.149 mm) increased from 0.50 to 4.01 mg/g at 25 °C, from 0.50 to 4.83 mg/g at 35 °C and from 0.50 to 4.19 mg/g at 45 °C, and the corresponding removal rates decreased from 99.97 to 40.10 % at 25 °C, 99.95 to 48.40 % at 35 °C and 99.92 to 42.05 % at 45 °C. At the initial concentrations of 5, 10 and 50 mg/L, the sorption capacities for the unpulverized PBGC-Fe/C sorbent (>3 mm) were determined to be 0.50, 0.99 and 2.49 mg/g, respectively, which exhibited a similar average value to those of fine particles or nanoparticles of iron oxides. The sorption could well be described by the pseudo-second-order kinetic equation. The equilibrium data were found to follow Freundlich as well as Langmuir isotherms.

Atmospheric deposition occurs in a variety of forms and is crucial for the evaluation of nutrient budgets, critical loads, and pollution inputs across space and time. Atmospheric wet deposition is typically quantified by analyzing the chemistry of precipitation that is collected in some type of container with a lid that opens in response to precipitation. However, collectors can vary in shape as well as in the sensor that signals when precipitation is occurring. Here, we compare the collectors made by Aerochem Metrics and N-CON Systems Company Inc. The former has been widely used for several decades, while the latter is relatively new and has been used in a variety of configurations depending on the solute of interest. Event-based samples were collected from August 2007 to October 2008 and analyzed for nitrate, ammonium, sulfate, chloride, and dissolved organic carbon (DOC). A variety of approaches were used to assess the comparability of the two collectors. Regressions of concentration versus concentration from the two collectors were strong, and the slope did not differ from 1 for nitrate, ammonium, or sulfate. The median concentrations of nitrate, ammonium, and sulfate were, however, significantly higher in the N-CON collector, while there were no overall differences between collectors for chloride or DOC. Although we have observed some statistically significant differences between solute concentrations of samples collected from the two collectors, our mixed results suggest that these differences are relatively small.

Rhizoremediation is a complex type of green clean-up technology that involves both plants and the rhizosphere-associated microorganisms to decompose hazardous compounds. The success of the strategy strongly depends on plant tolerance towards the pollutant, as well as plant's interactions with the rhizospheric microbes. The microorganisms may be stimulated by the secreted root exudates, which results in an increased breakdown of contaminants in the rhizosphere. The main goal of this study was to establish a potential rhizoremediation combination for a diesel-polluted site. Inoculation of plant roots or seeds with indigenous rhizospheric populations is a common approach in the rhizoremediation. However, we introduced hydrocarbon-degrading consortia (M10, R3, and K52) that were previously isolated from crude oil-contaminated soil instead of indigenous microbes. Bioaugmentation with these petroleum degraders was applied to screen four high biomass crop species (Indian mustard, alfalfa, high erucic acid rapeseed, HEAR, and low erucic acid rapeseed, LEAR) for their tolerance towards diesel oil. At no pollution, a promoting effect of M10 bacteria could be observed on germination and root elongation of all plant species. Moreover, M10 consortiums increased the germination index at 6,000 mg diesel oil per kilogram dry soil in the case of Indian mustard, alfalfa, and HEAR. The latter species was found to increment its dry weight upon bioaugmentation with M10 bacteria and all diesel oil treatments (6,000 and 24,000 mg diesel oil per kilogram dry soil). The initial results indicate HEAR and the M10 bacterial consortium as a promising plant-microbe tandem for a long-term rhizoremediation process. © 2013 The Author(s).

Chlorpyrifos (O, O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate) is a broad-spectrum organophosphate insecticide and acaricide, widely used in our country. Nowadays, it is the principal insecticide in the market employed for agricultural purposes. A number of studies tending to study the affinity of different pesticides with soil have been performed, but only a few refer to chlorpyrifos. Because of its intensive use, a wide range of terrestrial ecosystems may be contaminated with chlorpyrifos, and there is a need to evaluate its environmental behavior and effects. The aim of our work is to study the interaction and persistence of a commercial formulation of chlorpyrifos on an agricultural soil from Provincia de Buenos Aires, Argentina. In this case, recovery percentages increased with the increase of initial concentration of the pesticide until a concentration of about 25 ppm is reached, and then a decrease was observed. The half-time life was not affected by an increase in chlorpyrifos concentration.

As a polycyclic aromatic hydrocarbon (PAH), pyrene is one of hazardous persistent organic pollutants in the aquatic environment. The aim of this study was to investigate the influence of denitrifying conditions on pyrene degradation in a pure culture. With a strain isolated from petrol-contaminated river sediment, treatments of pyrene biodegradations were set up using various ratios of nitrate to nitrite (NO₃ ⁻/NO₂ ⁻). Results showed that various NO₃ ⁻/NO₂ ⁻ conditions significantly influenced the anaerobic pyrene degradation efficiency. Nitrite could induce the complete denitrification process so that NO₂ ⁻ acted as a key factor to promote high degradation efficiency. The low N treatment of NO₃ ⁻ and NO₂ ⁻ concentrations made the denitrifying-pyrene-degradation process more effective. Additionally, high C/N value stimulated high degradation rates. High concentrations of NO₃ ⁻ and NO₂ ⁻ as well as toxic intermediate product accumulation might inhibit the bacterial growth and biodegradation process. The information from this study should be useful to design bioremediation strategies of PAH.

Thus far, members of the genus Dehalococcoides are the only microorganisms known to dehalogenate chlorinated ethenes to ethene and thereby detoxify these common groundwater pollutants. Therefore, it is important to characterize the taxonomic and functional diversity of these key microorganisms and their reductive dehalogenase (RDase) genes in contaminated aquifers for assessing the natural attenuation potential. Little is known about the diversity of RDase genes under field conditions or in laboratory systems under selective pressure during dechlorination activities. Here, we evaluate the diversity of Dehalococcoides sp. and three RDase genes in groundwater as well as in water from a constructed wetland and microcosms setup with contaminated groundwater from the same field site in Bitterfeld (Saxony-Anhalt, Germany). The presence and relative abundance of Pinellas and Cornell subgroups of Dehalococcoides was evaluated by a novel direct sequencing method, which revealed that all sequences were identical and affiliated to the Pinellas subgroup. Contrarily, our results showed remarkable differences at the functional gene level between the systems. Of the vinyl chloride reductase genes, vcrA was detected in samples from the groundwater, wetland, and microcosms, whereas bvcA was only found in wetland and microcosm samples. The trichloroethene dehalogenase gene, tceA could not be detected at all, although complete dehalogenation activity of higher chlorinated ethenes was observed. Our study demonstrates that although the Dehalococcoides 16S rRNA gene sequences retrieved from the investigated systems were identical, the RDase gene diversity varied among the systems, according to the spectrum of the chlorinated ethenes present.

Land use in east China tends to change from paddy rice to vegetables or other high-value cash crops, resulting in high input rates of organic manures and increased risk of contamination with both heavy metals (HMs) and antibiotics. This investigation was conducted to determine the accumulation, distribution and risks of HMs and tetracyclines (TCs) in surface soils and profiles receiving different amounts of farmyard manure. Soil samples collected from suburbs of Hangzhou city, Zhejiang province were introduced to represent three types of land use change from paddy rice to asparagus production, vineyards and field mustard cultivation, and divided into two portions, one of which was air-dried and sieved through 2-, 0.3- and 0.149-mm nylon mesh for determination of pH and heavy metals. The other portion was frozen at -20 °C, freeze-dried and sieved through a 0.3-mm nylon mesh for tetracyline determination. HM and TC concentrations in surface soils of 14-year-old mustard fields were the highest with total Cu, Zn, Cd and ∑TCs of 50.5, 196, 1.03 mg kg(-1) and 22.9 μg kg(-1), respectively, on average. The total Cu sequence was field mustard > vineyards > asparagus when duration of land use change was considered; oxytetracycline (OTC) and doxycycline were dominant in soils used for asparagus production; OTC was dominant in vineyards and chlortetracycline (CTC) was dominant in mustard soils. There were positive pollution relationships among Cu, Zn and ∑TCs, especially between Cu and Zn or Cu and ∑TCs. Repeated and excessive application of manures from intensive farming systems may produce combined contamination with HMs and TCs which were found in the top 20 cm of the arable soil profiles and also extended to 20-40 cm depth. Increasing manure application rate and cultivation time led to continuing increases in residue concentrations and movement down the soil profile.

The electrochemical degradation of the Reactive Red 141 azo dye was done using a one-compartment filter-press flow cell with a boron-doped diamond anode. The response surface methodology (with a central composite design) was used to investigate the effect of current density (10–50 mA cm⁻²), pH (3–11), NaCl concentration ([NaCl]) (0–2.34 g L–¹), and temperature (15–55 °C) on the system’s performance. The charge required for 90 % decolorization (Q ⁹⁰), the fraction of chemical oxygen demand removal after 6 min of electrolysis (COD⁶), and the fraction of total organic carbon removal after 90 min of electrolysis (TOC⁹⁰) were used to model the obtained results. The lowest values of Q ⁹⁰ were attained at pH <4 in the presence of higher values of [NaCl] (>1.5 g L⁻¹), due to the electrogeneration of active chlorine, present mainly as HClO. The value of COD⁶ was not affected by the solution pH, but increased with [NaCl] up to 1.5 g L⁻¹. Higher temperatures (>40 °C) led to a decrease in COD⁶, as a consequence of side reactions. Higher values of TOC⁹⁰, which can be reached only with strong oxidants (such as ·OH and Cl·), were efficiently attained at low [NaCl] values (<0.7 g L⁻¹) in acidic solutions that inhibit the formation of ClO₃ ⁻ and ClO₄ ⁻. Finally, the obtained results allow inferring that most probably the mineralization of the dye starts with an attack on the chromophore group, followed by the degradation of intermediate species.

To assess strategies for mitigating Pb and As transfer into leafy vegetables from contaminated garden soils, we conducted greenhouse experiments using two field-contaminated soils amended with materials expected to reduce metal phytoavailability. Lettuce and mustard greens grown on these soils were analyzed by ICP-MS, showing that some Pb and As transfer into the vegetables occurred from both soils tested, but plant Pb concentrations were highly variable among treatment replicates. Soil-to-plant transfer was more efficient for As than for Pb. Contamination of the leaves by soil particles probably accounted for most of the vegetable Pb, since plant Pb concentrations were correlated to plant tissue concentrations of the immobile soil elements Al and Fe. This correlation was not observed for vegetable As concentrations, evidence that most of the soil-to-plant transfer for this toxic metal occurred by root uptake and translocation into the above-ground tissues. A follow-up greenhouse experiment with lettuce on one of the two contaminated soils revealed a lower and less variable foliar Pb concentration than observed in the first experiment, with evidence of less soil particle contamination of the crop. This reduced transfer of Pb to the crop appeared to be a physical effect attributable to the greater biomass causing reduced overall exposure of the above-ground tissues to the soil surface. Attempts to reduce soil Pb and As solubility and plant uptake by amendment at practical rates with stabilizing materials, including composts, peat, Ca phosphate, gypsum, and Fe oxide, were generally unsuccessful. Only Fe oxide reduced soluble As in the soil, but this effect did not persist. Phosphate amendment rapidly increased soil As solubility but had no measurable effect on either soil Pb solubility or concentrations of Pb or As in the leafy vegetables. The ineffectiveness of these amendments in reducing Pb transfer into leafy vegetables is attributed in this study to the low initial Pb solubility of the studied soils and the fact that the primary mechanism of Pb transfer is physical contamination.