Ozonation of azo dye Acid Red 14 in a microporous tube-in-tube microchannel reactor: decolorization and mechanism

Despite the great success of time-weighted average passive sampling of hydrophobic contaminants, such as PCBs and PAHs, the sampling of polar organic compounds still presents a challenge because the equilibrium between water and most sampling phases is attained in a relatively short time. In this study, we proposed a new time-integrative sampler using in situ solvent extraction (TISIS) for polar organic chemicals. The sampler was composed of a 15 cm poly(dimethylsiloxane) (PDMS) tubing, with an internal diameter of 0.5 mm and wall thickness of 0.5 mm, through which an extraction solvent (acetonitrile) was passed. Four polar organic contaminants, caffeine, atrazine, diuron and 17α-ethynylestradiol, were chosen for the evaluation of the performance of the sampler. Without the use of in situ solvent extraction, the PDMS tubing when exposed to a constant aqueous concentration of the four model compounds was able to linearly accumulate those compounds for less than 12 h and equilibrium between the PDMS tubing and water was attained in 2 d under our laboratory conditions. However, TISIS when exposed to a constant aqueous concentration was able to linearly accumulate all the model compounds without any exposure time limitation. The measured sampling rates at three different extraction flow rates (0.2, 0.5, 1.5 mL min⁻¹) were similar, regardless of the chemicals, indicating that the overall mass transfer from aqueous solution to the extraction solvent was most likely dominated by partitioning to the PDMS tubing and the internal diffusion within PDMS. In addition, a pulsed exposure experiment confirmed that TISIS operated in a time-integrative mode when the environmental concentration was highly fluctuated.     

3种不同工艺中莠灭净的去除特性及自由基鉴定

以三嗪类除草剂莠灭净（AMT）为目标污染物,对比研究了紫外（UV）、紫外激活过硫酸盐（UV/PS）与紫外激活过一氧硫酸氢盐（UV/PMS）3种不同工艺对AMT的去除效果以及反应动力学模型。考察了底物初始浓度、氧化剂浓度、溶液初始pH和水中腐殖酸浓度对AMT降解的影响,并对反应中生成的主要自由基进行鉴定。结果表明,3种系统下AMT降解均符合拟一级反应动力学模型（R2 ≥ 0.93）。AMT在3种不同系统下降解效率基本遵循UV/PS > UV/PMS > UV规律。随着底物初始浓度的增加,AMT降解率减小,拟一级速率常数kobs减小;增加氧化剂的投加量可以促进AMT降解;溶液pH的改变对UV系统下AMT的降解影响较小,而在UV/PS系统下,随着pH的增大降解率逐渐减小,在UV/PMS系统中降解率则呈现先减小后增大的趋势;投加腐殖酸会抑制AMT的降解;pH为7时,UV/PS和UV/PMS系统中反应生成的自由基主要是·SO4-。     

底物流加-间歇运行方式下氨氧化细菌富集培养的效果及影响因素分析

富集培养氨氧化细菌(AOB)可为污水处理工艺提高氨氮氧化速率、促进亚硝酸盐积累提供物质基础。在(20±2) ℃下,采用底物流加-间歇运行方式进行氨氧化细菌富集培养,重点考察了游离氨(FA)、游离亚硝酸(FNA)、溶解氧(DO)等因素的影响,并对富集前后活性污泥样品中的AOB进行了定性定量分析。结果表明：第15天左右AOB增殖进入稳定生长期,比氨氮氧化速率由接种时的4.45 mg·(g·h)⁻¹升高至57.22 mg·(g·h)⁻¹;通过pH、底物流加速率和实际反应速率关系的联合控制,可以实现整个反应过程中FA和FNA在预期范围内波动;即使在极低的DO条件下,高纯度的AOB也可进行氨氮氧化。高通量测序结果表明,体系内Nitrosomonas属的AOB大幅度增长,可由0.23%上升至54.18%,亚硝酸盐氧化细菌(NOB)的生长得到了有效抑制,培养结束时仅为0.12%。荧光定量PCR对AOB功能基因amoA的绝对含量结果表明,富集前后平均拷贝数由2.67×10⁵ copies·g⁻¹升至最大,可达9.67×10⁹ copies·g⁻¹,AOB成为活性污泥中的优势菌。本研究结果可为常温条件下快速富集AOB提供参考。     

Investigating the sources of the mutagenic activity found in a river using the Salmonella assay and different water extraction procedures

In the routine São Paulo state (Brazil) surface water quality-monitoring program, which includes the Salmonella microsome mutagenicity assay as one of its parameters, a river where water is taken and treated for drinking water purposes has repeatedly shown mutagenic activity. A textile dyeing facility employing azo-type dyes was the only identifiable source of mutagenic compounds. We extracted the river and drinking water samples with XAD4 at neutral and acidic pH and with blue rayon, which selectively adsorbs polycyclic compounds. We tested the industrial effluent, raw, and treated water and sediment samples with YG1041 and YG1042 and compared the results with the TA98 and TA100 strains. The elevated mutagenicity detected with YG-strains suggested that nitroaromatics and/or aromatic amines were causing the mutagenicity detected in the samples analyzed. Positive responses for the blue rayon extracts indicated that mutagenic polycyclic compounds were present in the water samples analyzed. The mutagen or mixture of mutagens present in the effluent and water samples cause mainly frameshift mutations and are positive with and without metabolic activation. The Salmonella assay combined with different extraction procedures proved to be very useful in the identification of the origin of the pollution and in the identification of the classes of chemical compounds causing the mutagenic activity in the river analyzed.     

The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

On the performance of Fe and Fe,F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the Blue Reactive 19 dye in simulated textile wastewater

The electrochemical performance of pure Ti–Pt/β-PbO₂ electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l⁻¹) was carried out under the following conditions: current density of 50 mA cm⁻², volume flow rate of 2.4 l h⁻¹, temperature of 25 °C and electrode area of 5 cm². The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l⁻¹ (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti–Pt/β-PbO₂–Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe³⁺ and 30 mM F⁻. In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure β-PbO₂ and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.     

A method for the determination of rhodamine b and brilliant sulfaflavine on cotton string collectors and in a spray tank solution mixture

Abstract

A fluorescent method for the determination of rhodamine B (RhB) and brilliant sulfaflavine (BSF) dual tracers on cotton string collectors and in spray tank solutions was developed for the evaluation of the effects of adjuvants on the atmospheric drift of agricultural sprays. Both tracers on collectors were extracted with deionized water simultaneously and measured directly with a Fluorescent Specrometer by switching the maximum excitation and emission wavelengths. The linear ranges of the RhB and BSF standard curves were 0–50 and 0–10 ppb respectively. Recoveries of tracers on cotton strings ranged from 92.9% ± 1.1% to 95.1% ± 1.0% for RhB and 91.9% ± 2.8% to 103% ± 0.6% for BSF when spiked levels ranged from 0.25 to 2.5 μg per collector. The detection limit of the instrument was approximately 0.1 ppb for both tracers. The detection limits of the analytical method were approximately 0.1 ppb for RhB and 0.3 ppb for BSF when the background levels of cotton strings were subtracted. The presence of one tracer in the solution did not significantly interfere with the detection of the other tracer in the same solution. The presence of adjuvants added to the spray tank solutions did not interfere with the detection of both tracers when the adjuvants were applied at the manufacturer's maximum recommendation rates.     

Hydroxyl radical concentration profile in photo-Fenton oxidation process: generation and consumption of hydroxyl radicals during the discoloration of azo-dye Orange II

Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H₂O₂ and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H₂O₂ and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H₂O₂ concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H₂O₂ concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.     

Automobile exhaust gas as a source of aqueous phase OH radical in the atmosphere and its effects on physiological status of pine trees

Free radical generation potential of automobile exhaust gas was examined by measuring hydroxyl (OH) radical photo-formation rates in exhaust gas-scrubbing water. Effects of automobile exhausts on physiological status of Japanese red pine trees (Pinus densiflora Sieb. et Zucc.) were also investigated to elucidate the mechanism how the free radicals derived from exhaust gas damage higher plants. Gasoline and diesel exhaust gases were scrubbed into pure water. Potential photo-formation rates of OH radical in aqueous phase (normalized to sun light intensity of clear sky midday on May 1 at 34°N) for gasoline and diesel cars were ave. 51 and 107 μM h⁻¹ m⁻³ of exhaust gas, respectively. Nitrite was a dominant source (ca. 70-90%) of photochemical formation of OH radical in both gasoline and diesel car exhausts. The scrubbed solution of diesel car exhaust gas was sprayed for six times per week to needles of pine tree seedlings in open top chambers. Control, exhaust + mannitol (added as OH radical scavenger), and nitrite + nitrate standard solution (equivalent levels existed in the exhaust gas) were also sprayed. Two months sprays indicated that the sprayed solutions of diesel exhaust and nitrite + nitrate caused a decrease of maximum photosynthetic rate and stomata conductance in pine needles while the control and exhaust + mannitol solution showed no effects on photosynthetic activities of pine needles. These results indicated that OH radicals generated mainly from photolysis of nitrite occurring in the scrubbing solution of exhaust gas are responsible for the decrease of photosynthetic activities of pine needles.     

某活性染料印染废水处理系统的优化改造

在充分调研的基础上 ,对一使用活性染料的印染厂的污水处理系统进行了改造 ,不仅使处理后废水主要污染指标达到国家污水排放一级标准 ,而且还有效地降低了运行费用 ,从而达到了优化系统的目的     

Simultaneous determination of fenitrothion and aminocarb in blueberry foliage and fruits: Application to the analysis of residues in field samples

Abstract

Samples of blueberry foliage and fruits were collected from spray blocks in Ontario after aerial application of fenitrothion and aminocarb at dosage rates of 210 g active ingredient (AI)/ha and 70 g AI/ha respectively. Residues were extracted from the samples by homogenizing with ethyl acetate, cleaned up by microcolumn chromatography using alumina as adsorbent, and analyzed by GLC‐AFID with a glass column packed with 1.5% OV‐17 and 1.95% OV‐210 on 80–100 mesh Chromosorb W‐HP. Average recoveries for fenitrothion and aminocarb from foliage at three fortification levels (1.0, 0.10 and 0.01 ppm) were respectively 99 and 96%. The corresponding values for the fruits were 99 and 95%. Foliage samples collected 1 h post‐spray contained on average 1.13 ppm of fe‐nitrothion and 1.14 ppm of aminocarb. However, residue levels reached below the detection limit (<0.01 ppm) in foliage collected 15 d after treatment. In addition, the fruit samples collected after 15 d post‐spray contained extremely low levels (0.03 ppm for fenitrothion and 0.02 ppm for aminocarb) of residues, and were barely above the detection limit.     

Pentachlorotoluene and pentabromotoluene: Results of a subacute and a subchronic toxicity study in the rat

Abstract

Pentachlorotoluene (PCT) and pentabromotoiuene (PBT) are environmental contaminants detected in the Great Lakes ecosystem. In view of the paucity of toxicity data and the potential for human exposure, a subacute (28 day) and a subchronic (91 day) study were conducted in the rat. In the subacute study, groups of 10 male and 10 female rats were fed the diet containing PCT or PBT at 0, 0.5, 5.0, 50 or 500 ppm for 28‐days. In the subchronic study, the group size was increased to 15, the dose levels were 0, 0.05, 0.5, 5.0, 50 and 500 ppm in the diet and the exposure period was 91 days. Growth rate and food consumption were not affected by exposure to either chemical in the subacute and subchronic study. Clinical observations revealed no abnormalities. Decreased hemoglobin was observed in female rats fed 5.0 ppm PCT and higher levels in the subacute (28 day) study. In the same study the hematocrit value and erythrocyte numbers of females fed 5.0 or 500 ppm PCT diets were significantly lower than the control. In both subacute and subchronic studies mild dose‐dependent histopathological changes were observed in the thyroid, liver and kidney of rats fed PCT and PBT diets. In general male rats were more susceptible than females to the treatment of PCT and PBT. Based on these data, it was concluded that the no observable adverse effect level for PCT was 50 ppm in the diet (3.5 mg/kg b.w./day) and that of PBT was 5.0 ppm (0.35 mg/kg b.w./day).     

Direct measurements of the tile drain and groundwater flow route contributions to surface water contamination: From field-scale concentration patterns in groundwater to catchment-scale surface water quality

Enhanced knowledge of water and solute pathways in catchments would improve the understanding of dynamics in water quality and would support the selection of appropriate water pollution mitigation options. For this study, we physically separated tile drain effluent and groundwater discharge from an agricultural field before it entered a 43.5-m ditch transect. Through continuous discharge measurements and weekly water quality sampling, we directly quantified the flow route contributions to surface water discharge and solute loading. Our multi-scale experimental approach allowed us to relate these measurements to field-scale NO₃ concentration patterns in shallow groundwater and to continuous NO₃ records at the catchment outlet. Our results show that the tile drains contributed 90-92% of the annual NO₃ and heavy metal loads. Considering their crucial role in water and solute transport, enhanced monitoring and modeling of tile drainage are important for adequate water quality management.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Estimating the potential of wild foods for nutrition and food security planning in tropical areas: Experimentation with a method in Northwestern Colombia

Wild foods contribute to the food security of multiple communities in tropical areas of Africa, Asia and Latin America. However, wild foods are not regularly considered in the planning of strategies for food and nutrition security mainly due to the lack of technical and/or scientific knowledge so that they can be considered suitable for human consumption. This paper proposes a multidisciplinary method that estimates the potential of wild foods as alternative resources when planning interventions in favour of food and nutrition security in tropical forest territories. When designing the method, four dimensions were identified in science, technology and innovation (STI) that define this potential as well as ten assessment criteria. The wild foods chosen for applying the method were Alibertia patinoi (a fruit commonly known as Borojó) and Proechimys semispinosus (Mouse of thorns), which are two of the main wild foods traditionally used by human communities in a tropical forest territory in the northwest of Colombia. In both cases, although there are significant advances in STI, compliance with some criteria is still required to regard them as viable alternatives for nutrition and food security within this territory. This research is useful for promoting the inclusion of wild food in food security programmes for communities where this food is already included in their traditional pattern of consumption and identifies the progress needed in STI to achieve this purpose. It may also promote the early recognition of possible traditional and cultural practices with high risk of transmission of pathogenic elements by the handling and/or inadequate consumption of wild foods. This early recognition could contribute to the prevention of diseases of wild animal origin, including those of rapid global spread.     

Simulation of a Hazardous and Noxious Substances (HNS) spill in the marine environment: Lethal and sublethal effects of acrylonitrile to the European seabass

Despite the extensive maritime transportation of Hazardous and Noxious Substances (HNS), there is a current lack of knowledge on the effects posed by HNS spills on the marine biota. Among the HNS identified as priority, acrylonitrile was selected to conduct ecotoxicological assays. We assessed the acute and subletal effects of acrylonitrile in seabass, followed by a recovery phase to simulate the conditions of a spill incident. The work aimed at testing a broad range of biological responses induced by acrylonitrile. Sublethal exposure to the highest two doses increased the fish mortality rate (8.3% and 25% mortality in 0.75 and 2 mg L⁻¹ acrylonitrile concentrations), whereas no mortality were observed in control and 0.15 mg L⁻¹ treatments. Additionally, important alterations at sub-individual level were observed. Acrylonitrile significantly induced the activities of Catalase– CAT and Glutathione S-Transferase – GST; and the levels of DNA damage were significantly increased. Conversely, Superoxide Dismutase– SOD – activity was found to be significantly inhibited and no effects were found on Lipid Peroxidation– LPO and ethoxyresorufin O-deethylase – EROD – activity. Following a 7 d recovery period, the levels of CAT, GST and EROD fell to levels at or below those in the control. In the 2 mg L⁻¹ group, SOD remained at the levels found during exposure phase. This study has gathered essential information on the acute and subletal toxicity of acrylonitrile to seabass. It also demonstrated that 7 d recovery allowed a return of most endpoints to background levels. These data will be useful to assist relevant bodies in preparedness and response to HNS spills.     

Levels of PCDD/Fs,PCBs and PBDEs in breast milk of women living in the vicinity of a hazardous waste incinerator: Assessment of the temporal trend

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in previous surveys carried out in the same area in 1998 (baseline study), 2002 and 2007. The current total concentrations of 2,3,7,8-chlorinated PCDD/Fs in breast milk ranged from 18 to 126 pg g⁻¹ fat (1.1–12.3 pg WHO₂₀₀₅-TEQ_PCDD/F), while the total levels of PCBs ranged from 27 to 405 pg g⁻¹ fat (0.7–5.3 pg WHO₂₀₀₅-TEQ_PCB). In turn, PBDE concentrations (sum of 15 congeners) ranged 0.3–5.1 g g⁻¹ fat, with a mean value of 1.3 ng g⁻¹ fat. A general decrease in the concentrations for PCDD/Fs, both planar and total PCBs, and PBDEs in breast milk was observed. The levels of PCDD/Fs, PCBs, and PBDEs in milk of women living in urban zones were higher than those corresponding to industrial zones (41%, 26%, and 8%, respectively). For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants that we have also observed in recent studies carried out in the same area of study.