Fate of a stilbene-type fluorescent whitening agent (DSBP) in the presence of Fe(III) aquacomplexes: from the redox process to the photodegradation

The behaviour of 4,4′-bis(2-sulfostyryl)biphenyl (DSBP), a fluorescent whitening agent, was investigated in the presence of Fe(III) aquacomplexes at room temperature. In the dark, a two-step reaction was observed when adding Fe(III) to a solution of DSBP: an initial fast redox reaction between DSBP and the monomeric species Fe(OH)²⁺ and a slower reaction leading to the coagulation of oxidised DSBP and iron. This phenomenon is due to the formation of a complex or an ion-pair between Fe(II) and/or Fe(III) with oxidised DSBP and it probably occurs by charge neutralisation in our experimental conditions. The precipitation of DSBP depends on the initial concentration in Fe(OH)²⁺ and is achieved for a ratio [Fe(OH) ²⁺]/[DSBP] of 5 approximately. Under irradiation at 365 nm, a complicated behaviour was observed: a complexation of iron by oxidised DSBP favoured by irradiation and a degradation of DSBP induced by an intramolecular electron transfer in the complex or by a photoredox of Fe(OH)²⁺ species generating OH radicals in the supernatant. The complete degradation of DSBP is reached four times faster in the presence of Fe(III) with respect to the direct photolysis of DSBP alone. Moreover, the total mineralization of DSBP obtained in less than 120 h upon irradiation at 365 nm is only observed in the presence of the ferric ions, enlightening the efficiency of the method involving Fe(III) and UV irradiation.     

Determination of 99Tc deposited on the ground within the 30-km zone around the Chernobyl reactor and estimation of 99Tc released into atmosphere by the accident

Technetium-99 was determined in samples from the 30-km zone around the Chernobyl reactor. Concentrations of ⁹⁹Tc in soil samples taken from three forest sites ranged from 1.1 to 14.1 Bq kg⁻¹ dry weight for the organic soil layers, and from 0.13 to 0.83 Bq kg⁻¹ dry weight for the mineral soil layers. In particular, for the organic layers, the measured ⁹⁹Tc concentrations were one or two orders of magnitude higher than those due to global fallout ⁹⁹Tc. The ⁹⁹Tc depositions (Bq m⁻²), based on the sum of the depositions measured in organic and mineral layers, ranged from 130 Bq m⁻² within the 10-km zone to about 20 Bq m⁻² close to the border of the 30-km zone. Taking the corresponding measured ¹³⁷Cs depositions into account, it was found that the activity ratio of ⁹⁹TW/¹³⁷Cs ranged from 6 × 10⁻⁵ to 1.2 × 10⁻⁴. It was estimated that about 970 GBq of ⁹⁹Tc had been released by the Chernobyl accident. This figure corresponded to 2%–3% of the total ⁹⁹Tc inventory in the core.     

Phytoremediation of radiostrontium ((90)Sr) and radiocesium ((137)Cs) using giant milky weed (Calotropis gigantea R.Br.) plants

Potential of plants to remove radionuclides/toxic elements from soils and solutions can be successfully applied for removal of important radionuclides such as strontium-90 (⁹⁰Sr) and cesium-137 (¹³⁷Cs). When uptake of ¹³⁷Cs and ⁹⁰Sr by Calotropis gigantea plants incubated in distilled water spiked with the radionuclides either alone or in combination was studied, it was found to have a high efficiency for the removal of ⁹⁰Sr, with 90% being removed from solutions (5 × 10³ kBq l⁻¹) within 24 h of incubation. However, in case of ¹³⁷Cs, about 44% could be removed from solutions (5 × 10³ kBq l⁻¹) at the end of 168 h of incubation. Accumulation of ⁹⁰Sr and ¹³⁷Cs was higher in roots compared to shoots. The plants could remediate both ⁹⁰Sr and ¹³⁷Cs when they were added together to the solution. When two months old plants were incubated in low level nuclear waste, 99% of activity disappeared at the end of 15 days. The present study suggests that C. gigantea could be used as a potential candidate plant for phytoremediation of ⁹⁰Sr and ¹³⁷Cs.     

The binding of three PCB congeners to dissolved organic carbon in freshwaters

The binding of three polychlorinated biphenyl (PCB) congeners to natural levels of dissolved organic carbon (DOC) was measured in 12 lakes and streams using Sep-Pak C₁₈ columns. The association coefficients calculated on the basis of DOC (i.e. K_DOC mL/g C), varied by over an order of magnitude among the different freshwaters and ranged between 2.05 × 10² and 8.86 × 10³ mL/g C for PCB 52 and 1.03 × 10⁴ and 1.70 × 10⁵ mL/g C for PCB 153. In general, there were no significant correlations (p > 0.05) between the K_DOC values and various chemical parameters in the study lakes and streams.

A relationship was derived between the fraction of bound PCB and the octanol-water partition coefficient. While this relationship explained almost 50% of the variation in the observed data, it is apparent that other factors influence K_DOC values and that in natural freshwaters, only a small fraction of the DOC is involved in the binding of PCBs and other hydrophobic pollutants.     

Distribution of DDT and benzo[a]pyrene between water and dissolved organic matter in natural humic water

DDT and benzo[a]pyrene (BaP) were added both separately and as a mixture to filtered (0.22 μm) humic surface water samples. Following a contact time of 1 d, the fraction bound to dissolved organic matter and the freely dissolved part were separated by using reversed-phase octadecyl silica cartridges. The enriched solutes were analysed by gas chromatography-mass spectrometry in the selective ion monitoring (GC-MS/SIM) mode. Partition coefficients to dissolved organic matter, calculated on the basis of the recovery data, varied between 2.0 × 10⁴ and 6.6 × 10⁴ mL/g for BaP depending on the experimental conditions, whereas the corresponding values for DDT (0.6 × 10⁴ mL/g) showed no significant variation.     

Use of pattern recognition in the evaluation of PCDD and PCDF residue data from GC/MS analyses

We used the chemometric approach with SIMCA (soft independent modeling by class analogy) multivariate statistical programs, based on principal components modeling to examine complex PCDD and PCDF residues in environmental samples. This approach was employed to determine the acceptability of measured tetrachloro isotope ratios when three ion intensities, m^+., (m+2)^+., and (m+4)^+., were measured by monitoring multiple ions. Isotope labeled internal standards and native compounds were examined. Principal components contain information about similarity of samples and variability in measurement. The data for the observed ion ratios were merged with the theoretical ion ratios and a calculated set of data that deviated from the theoretical values over a range of +/− 10 % for each ion pair. Thus the plot of principal components sample scores contains the error boundaries for accepting data that meet this quality assurance criterion and identifies the samples and calibration data that are within the acceptable range. In addition, GC/MS peaks having more than one constituent with different degrees of chlorination were readily detected. Residues of PCDDs in eggs of herring gulls ( ) collected from colonies in the Great Lakes region in 1981 – 1984 were measured by GC/MS. Principal components modeling of the normalized residue data demonstrated that the sample residue profiles differed according to the sample's origin and that sample profiles remained remarkably similar over the 4-year period in which the samples were collected.     

Studying soil organic matter using 13C CP-MAS NMR: the effect of soil chemical pre-treatments on spectra quality and representativity

¹³C CP-MAS NMR spectroscopy is a technique that has proved to be useful in studying soil organic matter (SOM). Nevertheless, NMR spectra exhibit a weak signal and have very low resolution due to: the low natural abundance of ¹³C (1.1 % of C) in SOM, the generally low SOM content of soils, and the presence of paramagnetic impurities. This paper studies the effects of soil chemical pre-treatments on ¹³CP-MAS NMR spectra quality and spectra representativity i.e. soil C mass balance.

After chemical pre-treatment to increase total organic carbon (TOC) content and C/Fe ratio, eight soils characterized by different levels of organic carbon content and C/Fe ratios were studied using ¹³CP-MAS NMR. Moreover, where chemical treatments were not applicable due to high carbon losses, the number of ¹³CP-MAS NMR scans was increased in order to obtain satisfactory spectra.

Results show that chemical pre-treatment of soils with C/Fe > 1 caused high C losses. Bulk soils were therefore studied by increasing the number of ¹³CP-MAS NMR scans. Acceptable spectra were obtained from 8K scans (1K = 1024 transient). On the other hand, even when a large number of scan (32K) are used, soil with C/Fe < 1 cannot be studied. As these soils are characterized by low C losses after HCl treatments (range of 2.9–25.4%), a pre-treatment of at least 1.39 mol l⁻¹ HCl removes excess Fe and at the same time increases C/Fe ratio resulting in 32K scans providing good spectra.     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

As(V) adsorption on amorphous iron oxide: Triple layer modelling

The adsorption of As(V) by amorphous iron oxide was investigated at 25°C, 0.01 M NaNO₃ background electrolyte as a function of solution pH(4–10) at three initial As(V) concentrations and two Fe(III) concentrations. As(V) adsorption increased with decreasing pH. A modified Langmuir isotherm has been used for describing an equilibrium partition existing between solid and liquid phases. The triple-layer model was used for simulating As(V) adsorption on iron oxide surface. This model was able to describe As(V) adsorption over the pH range 4–10, all at the concentrations of As(V) and Fe(III) studied. =Fe(H₂AsO₄)⁰, = Fe(HAsO₄)⁻ and = Fe(AsO₄)²⁻ have been shown through simulation with inner-sphere complexation products to be more consistent with experimental adsorption observations than complexation with other surface species.     

Relationship between electron donor and microorganism on the dechlorination of carbon tetrachloride by an anaerobic enrichment culture

An investigation involving the supplement of different concentrations of substrates and microorganisms was carried out under anaerobic condition to assess the feasibility of bioremediation of carbon tetrachloride (CCl₄) with the amendment of low concentrations of auxiliary substrate and microorganisms. The concentrations of substrate and microorganisms ranged from 10 to 100 mg/l and from 3.7 × 10⁴ to 3.7 × 10⁶ cell/ml, respectively. The biotransformation rate of CCl₄ increased progressively with the increase in the concentrations of the substrate and microorganisms. In the low biomass-amended system (3.7 × 10⁴cells/ml), 28–71% and 57–96% of CCl₄ removals were exhibited when 10–100 mg/l of acetate or glucose was supplemented, respectively, whereas nearly complete degradation of CCl₄ was observed in the heavily inoculated systems (3.7 × 10⁶ cells/ml). An addition of electron donor in the low microbial activity batches enhanced greater efficiency in dechlorination than in the high microbial activity batches. The second-order rate constants ranged from 0.0059 to 0.0092 l/mg/day in high biomass input system, while a two- to four-fold increase in rate constant was obtained in the low microbial activity system. This study indicates that biomass was the more important environmental parameter than substrate affecting the fate of CCl₄. The addition of auxiliary substrates was effective only in low biomass-amended batches (0.56 mg-VSS/l) and diminished inversely with the increase of microbial concentration.     

Nonylphenols in freshwaters of the hydrologic system of an Italian district: association with human activities and evaluation of human exposure

A sampling campaign for the determination of concentrations of nonylphenol isomers (NPs) in freshwaters and sediments of the hydrologic system of the Rieti district (central Italy) was conducted from 2002 to 2003. Eighteen sampling points, selected on the basis of the different human activities in the vicinity, were monitored; six series of water samples (from June 2002 to February 2003) and one of sediment samples (summer 2002) were analyzed by GC/MS.

There was a direct relationship between concentrations of NPs and the presence of urban or industrial activities near the sampling point. However, concentrations of NPs in water were in the range of <0.1–1.4 μg l⁻¹, and their presence limited to short distances from the sources of contamination. Accumulation factors in sediment samples ranged from 10² to 5 × 10³.     

Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

湖北省能源消费CO2与大气污染物协同减排研究

以2015年为基准年,基于拓展的STIRPAT模型预测2025年湖北省能源消费CO2和主要大气污染物排放量.通过设置基准(记为BAU)情景、低碳(记为LC)情景和强化低碳(记为ELC)情景3种控制情景,测算CO2和主要大气污染物的减排量,并运用污染物减排量交叉弹性法评价了CO2减排对主要大气污染物的协同效应.结果表明,...     

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.     

Fe and UV-enhanced ozonation of chlorophenolic compounds in aqueous medium

Mono-, di- and trichlorophenol including different isomers were degraded by O₃, O₃ + UV and O₃ + UV + Fe³⁺. Disappearance rates are nearly identical among three ozonations. Whereas TOC elimination was not completed by ozone alone. UV illumination accelerated TOC elimination rate and the addition of Fe³⁺ (O₃ + UV + Fe³⁺) further accelerated it. TOC elimination rates among different chlorophenols were in the order of mono > di > tri. The effect of Fe³⁺ was largest on the degradation of trichlorophenol. Hydroxylated aromatics, organic acids, formaldehyde and acetone were detected as intermediates.     

Determination of vapour pressures of nine organic chemicals adsorbed on silicagel

The vapour pressures of nine organic chemicals adsorbed on silicagel were determined by a method which can be standardized. They were compared with those of the non-absorbed, free compounds (range 6 × 10⁻³ – 7 × 10⁴ Pa).     

The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

Influence of water hardness on the bioavailability and toxicity of linear alkylbenzene sulphonate (LAS)

In the present work, the influence of Ca²⁺ concentration on the toxicity of single cut linear alkylbenzene sulfonate (LAS) homologues was studied. Precipitation boundary diagrams for each homologue were obtained, indicating turbid and clear zones depending on the LAS and Ca²⁺ concentrations. The separation between transparent and turbid zones is given by the so-called precipitation line. LAS toxicity to Daphnia magna was determined at concentrations close to this precipitation line. It was observed that when Ca(LAS)₂ precipitation progresses, LAS bioavailability decreases for test animals, and the toxicity diminishes even at high nominal LAS concentrations. According to the “free ion activity model” (FIAM), the toxicity of a given chemical compound is mainly due to the ionic species (Ca²⁺–LAS⁻) and not due to the precipitated molecule, Ca(LAS)₂. The significance of the present study is in connection with the assessment of LAS sorption/precipitation studies in soils and sediments, where in situ toxicity is strongly influenced by Ca²⁺/Mg²⁺ ions, according to the results presented in this work.     

Synchronous-scan fluorescence spectra of Chlorella vulgaris solution

The characterization of the Chlorella vulgaris solution was carried out using synchronous-scan spectroscopy. The range of concentration of algae and Fe(III) in aqueous solutions were 5 × 10⁸–8 × 10⁹ cells l⁻¹ and 10–60 μM, respectively. Effective characterization method used was synchronous-scan fluorescence spectroscopy. The wavelength difference (Δλ) of 90 nm was maintained between excitation and emission wavelengths; 90 nm was found to be the best Δλ for effective characterization of Chlorella vulgaris solution with or without quencher species (e.g., Fe(III), humic acid (HA)) for the first time. The peak was observed at about EX 236.6 nm/EM 326.6 nm for synchronous-scan fluorescence spectra. The fluorescence quenching of algae in system of algae–Fe(III)–HA was studied using synchronous-scan spectroscopy for the first time. Fe(III) was clearly the effective quencher. The relationship between I₀/I (quenching efficiency) and c (concentration of Fe(III) added) was a linear correlation for the algae solution with Fe(III). Also, Aldrich humic acid was found to be an effective quencher. pH effect on synchronous-scan fluorescence intensity of algal solution with Fe(III) and/or HA was evident.