HQSAR and CoMFA approaches in predicting reactivity of halogenated compounds with hydroxyl radicals

Two quantitative structure–activity relationship (QSAR) methods: hologram QSAR (HQSAR) and comparative molecular field analysis (CoMFa) were evaluated for predicting half-lives of the hydroxyl radicals reaction with substituted aromatic compounds. The HQSAR approach, which is topological in nature, results in a mathematical model which was more stable and has a greater predictive ability than the model derived on the 3-D CoMFA approach. Interpretations of the colour coded results of both methods are in good agreement with the proposed mechanism of the hydroxyl radical oxidation of halogenated aromatic compounds in the atmosphere.     

Development of QSARs to investigate the bacterial toxicity and biotransformation potential of aromatic heterocylic compounds

A series of aromatic heterocyclic and hydrocarbon compounds were tested for toxicity and biotransformation potential against two contrasting lux-marked whole-cell microbial biosensors. Toxicity was determined by inhibition of light output of a Pseudomonas fluorescens construct that expresses lux constitutively. Biotransformation was tested by increase in light output of P. fluorescens HK44 (pUTK21), which expresses lux when in the presence of a metabolic intermediate (salicylate). The data were then modelled against physical/chemical properties of the compounds tested to see if quantitative structure–activity relationships (QSARs) could be derived. Toxicity was found to be accurately predicted by log K_ow (R²=0.95, Q²=0.88), with the basic (pyridine-ring containing) heterocycles modelled separately. The biotransformation data were best modelled using lowest unoccupied molecular orbital (LUMO) energies (R²=0.90, Q²=0.87).     

Bioavailability of zinc in runoff water from roofing materials

Corrosion and runoff from zinc-coated materials and outdoor structures is an important source for the dispersion of zinc in the environment. Being part of a large inter-disciplinary research project, this study presents the bioavailability of zinc in runoff water immediately after release from the surface of 15 different commercially available zinc-based materials exposed to the urban environment of Stockholm, Sweden. Runoff water was analysed chemically and evaluated for its possible environmental impact, using both a biosensor test with the bacteria Alcaligenes eutrophus (Biomet^®) and the conventional 72 h growth inhibition test with the green alga Raphidocelis subcapitata. Chemical speciation modelling revealed that most zinc (94.3–99.9%) was present as the free Zn ion, the most bioavailable speciation form. These findings were confirmed by the results of the biosensor test (Biomet^®) which indicated that all zinc was indeed bioavailable. Analysis of the ecotoxicity data also suggested that the observed toxic effects were due to the presence of Zn²⁺ ions. Finally, regression analysis showed that, for this type of runoff samples, the rapid screening biosensor was capable of predicting (a) the total amount of zinc present in the runoff samples (R² of 0.93–0.98; p<0.05) and (b) the observed 72 h-EbC₅₀s (R² of 0.69–0.97; p<0.05).     

Kinetic studies of adsorption of thiocyanate onto ZnCl2 activated carbon from coir pith, an agricultural solid waste

The adsorption of thiocyanate onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of various parameters such as agitation time, thiocyanate concentration, adsorbent dose, pH and temperature has been studied. Adsorption followed second-order rate kinetics. Two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q₀) was found to be 16.2 mg g⁻¹ of the adsorbent. The per cent adsorption was maximum in the pH range 3.0–7.0. pH effect and desorption studies showed that ion exchange and chemisorption mechanism are involved in the adsorption process. Thermodynamic parameters such as ΔG⁰, ΔH⁰ and ΔS⁰ for the adsorption were evaluated. The negative values of ΔH⁰ confirm the exothermic nature of adsorption. Effects of foreign ions on the adsorption of thiocyanate have been investigated. Removal of thiocyanate from ground water was also tested.     

Impacts of simulated acid rain on cation leaching from the Latosol in south China

Acid rain is a problem of increasing agricultural, environmental, and ecological concerns worldwide. This study investigated impacts of simulated acid rain (SAR) on cation leaching from the Latosol in south China. Latosol is an acidic red soil and occurs in the tropical rainforest biome. Laboratory experiments were performed by leaching the soil columns with the SAR at a pH range from 2.5 to 7.0 over a 21-day period. A linear increase in effluent K⁺ concentration was found at the SAR pH 3.0, whereas an exponential decrease in effluent Na⁺ concentration was observed at all levels of the SAR pH. In general, leaching of Ca²⁺ and Mg²⁺ from the Latosol increased as the SAR pH decreased. There was a very good nonlinear correlation between the removal of soil K⁺ and the SAR pH (R² = 0.91), a good nonlinear correlation between the removal of soil Mg⁺² and the SAR pH (R² = 0.83), a fairly good nonlinear correlation between the removal of soil Ca⁺² and the SAR pH (R² = 0.56), and no correlation between the removal of soil Na⁺ and the SAR pH (R² = 0.06). Our study further revealed that the removal of soil cations such as K⁺, Ca⁺², and Mg⁺² can be quantified by the quadratic polynomial equations. In addition, impacts of the SAR on cation leaching depended not only on the SAR pH but also on the original soil pH.     

Impacts of some meteorological parameters on SO2 and TSP concentrations in Erzurum, Turkey

The air pollution is the one of the most important environmental problems in Erzurum, situated in the eastern of Turkey, during winter periods. The unfavorable climate as well as the city’s topography, and inappropriate urbanization cause serious air pollution problems. The air pollutant concentrations in a city have a close relationship with its meteorological parameters. In the present study, the relationship between daily average total suspended particulate (TSP) and sulphur dioxide (SO₂) concentrations with meteorological factors, such as wind speed, temperature, relative humidity, pressure and precipitation, in 1995–2002 winter seasons was statistically analyzed using the stepwise multiple linear regression analysis. According to the results obtained through analysis, higher TSP and SO₂ concentrations are strongly related to colder temperatures, lower wind speed, higher pressure system and weakly lower precipitation and higher relative humidity. The statistical models of SO₂ and TSP including meteorological parameters gave R² of 0.74 and 0.88, respectively. Furthermore, the correlation between the previous day’s SO₂, TSP concentrations and actual concentrations of these pollutants on that day was investigated and found as 0.84 and 0.53, respectively. In order to develop this model, previous day’s SO₂ and TSP concentrations were added to the equations. The new model for SO₂ enhanced considerably (R² = 0.92), but for TSP new model was not enhanced (R² = 0.89).     

The toxicity of copper,cadmium and zinc to four different Hydra (Cnidaria: Hydrozoa)

An acute toxicity study of three metals to Hydra species carried out using two different assessment methods, (i) determination of the LC50 and (ii) measurement of progressive morphological changes, demonstrated that relative toxicity decreased from copper to cadmium with zinc the least toxic for all species. The latter method revealed more details of the effect on Hydra in terms of physical damage to the polyp but both methods indicated that H. viridissima was more sensitive to copper and cadmium than H. vulgaris¹ (Zurich strain, male clone), H. vulgaris² (a dioecious strain reproducing sexually and asexually) and H. oligactis (dioecious, reproducing sexually and asexually). The responses to zinc were similar for all Hydra. The possible role of metabolic interactions between H. viridissima and its symbiotic green algae in contributing to the greater sensitivity of this polyp is discussed.     

Comparison of screening methods for the estimation of adsorption coefficients on soil

The HPLC screening method for estimating soil sorption coefficients was compared to other QSAR approaches based on log P_ow, connectivity indices, molar refraction and molecular fragment approaches. For the data set under consideration (66 compounds from different chemical classes) only the HPLC screening method and, to a lesser extend, the log P_ow method proved to be suitable for predicting soil sorption coefficients with acceptable accuracy. The HPLC method and the regression with log P_ow were then cross-validated.     

Characterizing As(III,V) adsorption by soils surrounding ash disposal facilities

Leachate derived from unlined coal ash disposal facilities is a potential anthropogenic source of arsenic to the environment. To establish a theoretical framework for predicting attenuation of arsenic by soils subject to ash landfill leachate, which is typically enriched in calcium and sulfate, the adsorption of As(V) and As(III) was characterized from 1 mM CaSO₄ for 18 soils obtained down-gradient from three ash landfill sites and representing a wide range in soil properties. As(V) consistently exhibited an order of magnitude greater adsorption than As(III). As(V) adsorption was best described by coupling pH with 15 s DCB-Fe (R² = 0.851,  = 0.001), although pH coupled to clay, DCB-Fe, or DCB-Al also generated strong correlations. For As(III), pH coupled to Ox–Fe (R² = 0.725,  = 0.001) or Ox–Fe/Al (R² = 0.771,  = 0.001) provided the best predictive relationships. Ca²⁺ induced increases in As(V) adsorption whereas sulfate suppressed both As(V) and As(III) adsorption. Attenuation of arsenic from ash leachate agreed well with adsorption measured from 1 mM CaSO₄ suggesting that the use of 1 mM CaSO₄ in laboratory adsorption tests is a reasonable approach for estimating arsenic behavior in soils surrounding ash landfills. We also showed that the impact of leachate-induced changes in soil pH over time may not be significant for As(V) adsorption at pH < 7; however, As(III) adsorption may be impacted over a wider pH range especially if phyllosilicate clays contribute significantly to adsorption. The benefits and limitations of predicting arsenic mobility using linearized adsorption coefficients estimated from nonlinear adsorption isotherms or from the relationships generated in this study are also discussed.     

Experimental determination of the kinetic rate law for the oxidation of perchloroethylene by potassium permanganate

Flushing soils contaminated with trichloroethylene (TCE) and perchloroethylene (PCE) with a permanganate (MnO₄⁻) solution has been shown to reduce the solvent content of the soil. Experiments were performed to quantify the rate at which KMnO₄ oxidizes aqueous solutions of PCE over a range of concentrations. In a series of homogeneous reactors, aqueous phase PCE concentrations were monitored over time in nine experimental trials with excess oxidant concentrations ranging from 5 to 30 g/l. Analysis of the data was performed to quantify the oxidation reaction order with respect to PCE and KMnO₄ and the reaction rate constant. The reaction between PCE and KMnO₄ was determined to be first-order with respect to both PCE and KMnO₄ with an overall specific reaction rate coefficient of 2.45±0.65 M⁻¹ min⁻¹.     

The influence of storage on the morphology and physiology of phthalic acid-degrading aerobic granules

The precultured aerobic granules with special degradabilities could be used as a feasible bioseed for enhancement of aerobic granulation systems. In practice, the storage stability, physicochemical characteristics, and recovering efficiency of granules are crucial for a long-distance transportation and successful application. In this study, phthalic acid (PA)-degrading aerobic granules were cultivated and stored for 8 wk at 4 °C. The granular size, settling ability as well as structure integrity was found stable during the storage period. It was observed that the upper 1/3 part of granules stored in the reagent bottle turned to black color, while the lower 2/3 part granules did not significantly change color (brown–yellow) after the 8-wk storage. The black and brown–yellow color PA-degrading granules were manually separated and re-inoculated into two identical sequencing batch reactors for reviving the PA degradation capability. After a 7 d operation, both black and yellow granules restored their activities to the levels before storage, in terms of total organic carbon removal efficiency (100%), specific oxygen uptake rate (59 mg g VSS⁻¹ h⁻¹), and adenosine triphosphate content (0.016 mg g VSS⁻¹). This study demonstrated that aerobic granules grown on a complex substrate could tolerate storage conditions and rapidly restored their bioactivities toward the target pollutant. The results also shed the light on the future application of precultured aerobic granules with unique functions for biodegradation and bioremediation purpose.     

An investigation of adsorption at the air-water and soil-water interfaces for non-micellizing ethylene oxide-propylene oxide surfactants

Adsorption at the air–water interface and soil sorption from aqueous solution have been investigated for a group of ethylene oxide (EO)–propylene oxide (PO) block copolymeric surfactants. The group which have a common structural formula of EO_m PO_n EO_m is distinguished by the fact that they have large critical micelle concentration (CMC) values and therefore do not readily form micelles at common environmental concentrations and temperatures. Adsorption at the air–water interface is readily shown to be driven by the size of the hydrophobic PO block. The size of the reduction in surface tension produced by a common concentration of 10⁻⁵ mol dm⁻³ linearly increases with the size of the PO block as does the efficiency of adsorption at the air–water interface as measured by pC₂₀ – the negative logarithm of the surfactant concentration that produces a reduction in surface tension of 20 mN m⁻¹. Soil sorption data have also been captured for these compounds and the data are readily fitted to the Freundlich adsorption isotherm. However soil sorption is shown to be inversely related to the molecular mass of the molecules and appears to be related to the size of the hydrophilic EO blocks in the molecule.     

染料结构-光催化降解活性关系初步研究

以近20种水溶性染料为研究对象,选择正辛醇-水分配系数(Kow)、分子最高占据轨道能(EHOMO)及分子最低空轨道能(ELUMO)等理化参数,建立了染料的定量结构-光催化降解反应活性关系模型,得到定量关系式为:lgk＝0.016 28×lgKow 0.132 46×(ELUMO-EHOMO)-2.148 56,很好地表示反应活性与结构之间的定量关系,为水溶性染料的光催化降解活性预测提供了有效的工具.     

Quantitative structure-activity relationship (QSAR) models for polycyclic aromatic hydrocarbons (PAHs) dissipation in rhizosphere based on molecular structure and effect size

Rhizoremediation is a significant form of bioremediation for polycyclic aromatic hydrocarbons (PAHs). This study examined the role of molecular structure in determining the rhizosphere effect on PAHs dissipation. Effect size in meta-analysis was employed as activity dataset for building quantitative structure-activity relationship (QSAR) models and accumulative effect sizes of 16 PAHs were used for validation of these models. Based on the genetic algorithm combined with partial least square regression, models for comprehensive dataset, Poaceae dataset, and Fabaceae dataset were built. The results showed that information indices, calculated as information content of molecules based on the calculation of equivalence classes from the molecular graph, were the most important molecular structural indices for QSAR models of rhizosphere effect on PAHs dissipation. The QSAR model, based on the molecular structure indices and effect size, has potential to be used in studying and predicting the rhizosphere effect of PAHs dissipation.     

Biodegradation kinetics and toxicity of vegetable oil triacylglycerols under aerobic conditions

The aerobic biodegradation of five triacylglycerols (TAGs), three liquids [triolein (OOO), trilinolein (LLL), and trilinolenin (LnLnLn)] and two solids [tripalmitin (PPP) and tristearin (SSS)] was studied in water. Respirometry tests were designed and conducted to determine the biochemical oxygen demand (BOD) parameters of the compounds. In the case of the solid lipids, the degradation process was limited by their extremely non-polar nature. When added to water, PPP and SSS formed irregular clumps or gumballs, not a fine and uniform suspension required for the lipase activity. After 30 days, appreciable mineralization was not achieved; therefore, first-order biodegradation coefficients could not be determined. The bioavailability of the liquid TAGs was restricted due to the presence of double bonds in the fatty acids (FAs). An autoxidation process occurred in the allylic chains, resulting in the production of hydroperoxides. These compounds polymerized and became non-biodegradable. Nevertheless, the non-oxidized fractions were readily mineralized, and BOD rate constants were estimated by non-linear regression: LLL (k = 0.0061 h⁻¹) and LnLnLn (k = 0.0071 h⁻¹) were degraded more rapidly than OOO (k = 0.0025 h⁻¹). Lipids strongly partitioned to the biomass and, therefore, Microtox^® toxicity was not observed in the water column. However, EC₅₀ values (<15% sample volume) were measured in the solid phase.     

Sequential photochemical-biological degradation of chlorophenols

UV/TiO₂/H₂O₂, UV/TiO₂ and UV/H₂O₂ were compared as pre-treatment processes for the detoxification of mixtures of 4-chlorophenol (4CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) prior to their biological treatment. When each chlorophenol was initially supplied at 50 mg l⁻¹, UV/TiO₂/H₂O₂ treatment supported the highest pollutant removal, COD removal, and dechlorination efficiencies followed by UV/TiO₂ and UV/H₂O₂. The remaining toxicity to Lipedium sativum was similar after all pre-treatments. Chlorophenol photodegradation was always well described by a first order model kinetic (r² > 0.94) and the shortest 4CP, DCP, TCP and PCP half-lives of 8.7, 7.1, 4.5 and 3.3 h, respectively, were achieved during UV/TiO₂/H₂O₂ treatment. No pollutant removal was observed in the controls conducted with H₂O₂ or TiO₂ only. Inoculation of all the photochemically pre-treated mixtures with activated sludge microflora was followed by complete removal of the remaining pollutants. Combined UV/TiO₂/H₂O₂-biological supported the highest detoxification, dechlorination (99%) and COD removal (88%) efficiencies. Similar results were achieved when each chlorophenol was supplied at 100 mg l⁻¹. COD and Cl mass balances indicated UV, UV/H₂O₂, and UV/TiO₂ treatments lead to the formation of recalcitrant photoproducts, some of which were chlorinated.