Model reactor for photocatalytic degradation of persistent chemicals in ponds and waste water

A laboratory scale flow-through model reactor for the degradation of persistent chemicals using titanium dioxide (TiO₂) as photocatalyst immobilized on glass beads is presented. In the test system with a volume of 18 L contaminated water is pumped to the upper part of the floating reactor and flows over the coated beads which are exposed to UV-radiation. The degradation of two dyes of different persistance was investigated. Primary degradation of methylene blue did not fit a first order kinetic due to coincident adsorption onto the photocatalyst and direct photolysis, resulting in a half-life of 6 h. A filtrate of a green algae suspension accelerated the colour removal. In contrast, reactive red 2 was degraded only by photocatalysis; neither adsorption nor direct photolysis led to a colour removal. The course of primary degradation followed a first order kinetic with a half-life of 18 h and a rate constant of 0.04 h⁻¹. Analysis of the degradation products indicated mineralization by detection of NO₂⁻ and NO₃⁻, accompanied by a decrease of pH and an increase of conductivity. A successful adaptation of the model reactor (scale 1:10) to dimensions required for surface waters and waste water treatment plants would be a costefficient and environmentally sustainable application of photocatalysis for the treatment of industrially polluted water and could be of relevance for third world contries, particularly those favoured by high solar radiation.     

Biodegradation of nonylphenol in sewage sludge

We investigated the effects of various factors on the aerobic degradation of nonylphenol (NP) in sewage sludge. NP (5 mg/kg) degradation rate constants (k₁) calculated were 0.148 and 0.224 day⁻¹ for the batch experiment and the bioreactor experiment, respectively, and half-lives (t_1/2) were 4.7 and 3.1 days, respectively. The optimal pH value for NP degradation in sludge was 7.0 and the degradation rate was enhanced when the temperature was increased and when yeast extract (5 mg/l) and surfactants such as brij 30 or brij 35 (55 or 91 μM) were added. The addition of aluminum sulfate (200 mg/l) and hydrogen peroxide (1 mg/l) inhibited NP degradation within 28 days of incubation. Of the microorganism strains isolated from the sludge samples, we found that strain CT7 (identified as Bacillus sphaericus) manifested the best degrading ability.     

Dechlorination of 1,2,4-trichlorobenzene in the sediment of Ise Bay

The relation between dechlorination activities of 1,2,4-trichlorobenzene and anaerobic microbial activity were studied in the sediment collected at three sites in Ise Bay in Japan. The degradation rate of spiked 1,2,4-trichlorobenzene (3nmol ml⁻¹) ranged from 15 to 35 pmol day⁻¹ ml⁻¹ wet sediment and about 1/3 to 1/2 of degraded the trichlorobenzene was recovered as dechlorinated products. Among the dichlorobenzenes, the 1,2-isomer had the highest and 1,3-isomer had the lowest production rate. Comparing the three sampling sites, the trichlorobenzene degradation and dichlorobenzenes production rates were related to the sulfate reducing activity for the unit number of sulfate reducing bacteria. Production rates of dichlorobenzenes were completely inhibited by adding molybdate (20 mM), nitrate (60 mM), and formaldehyde solution (4 %). These results indicated that dechlorination activity in the Ise Bay sediment was supported by sulfate reduction activity in the sediment, and not supported by any other anaerobic microbial activity.     

呼吸法测定硝化菌产率系数实验研究

基于硝化过程中合成代谢和能量代谢耦合原理,分析硝化过程中的电子流,建立自养硝化菌细胞生长与氨氮氧化耗氧量之间的关系。采用间歇实验方法,通过电解质呼吸仪测定硝化过程的累积耗氧量和耗氧速率,使用M ann-Ken-dell趋势检验方法确定实验中硝化菌进入内源呼吸的时刻以及内源呼吸过程中的耗氧速率,估算出氨氮氧化的耗氧量。计算结果表明本实验中硝化菌产率系数为0.2345±0.0115 mg COD/mg NH4+-N。     

固定化降解菌Q5去除喹啉的性能研究

为了研究固定化微生物在土壤生物修复中的应用,以实验室筛选出来的高效降解菌 Q5 为生物活性物质,利用生物大分子仿生合成出的纳米多孔氧化硅为载体,通过表面吸附同定化方法将其固定,制备出固定化微生物.考察固定化微牛物初始 pH 值、温度、摇床转速和菌种的接种量对喹啉去除的影响,得到适宜的去除条件,在相同条件下比较固定化微生物与游离菌种对底物的去除情况,研究单一固定化菌种对不同浓度的喹啉的去除情况,考察固定化微生物的稳定性.实验结果表明,菌株 Q5 经固定化后,对喹啉的去除能力大大增强,在 500 mg/L 浓度下,40 h 固定化 Q5 对底物去除率达96.6%,远高于未固定化 Q5 的去除率 56.1%;对于高底物浓度,固定化微生物的去除效果明显,初始底物浓度为1 500 mg/L,反应 70 h 后去除率为 91.6%,且这种固定化微生物的重复使用性能良好.     

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

The opposing effects of bacterial activity and gas production on anaerobic TCE degradation in soil columns

This laboratory study explores the effect of growth substrate concentration on the anaerobic degradation of trichloroethylene (TCE) in sand packed columns. In all columns the growth substrate rapidly degraded to gas, that formed a separate phase. Biomass accumulated in the 0–4.8 cm section of the columns in proportion to the influent growth substrate concentration and biomass concentrations in the remaining sections of all columns were similar to the column receiving the lowest substrate concentration. Increases in growth substrate concentration up to 3030 mg-COD l⁻¹ promoted TCE degradation, but a further increase to 14 300 mg-COD l⁻¹ reduced the amount of TCE completely dechlorinated but did not affect the production of chlorinated TCE intermediates. The mathematical model developed here satisfactorily described the enhancement in TCE dehalogenation for substrate concentration up to 3030 mg-COD l⁻¹; reproducing TCE dehalogenation for 14 300 mg-COD l⁻¹ required that the moisture content used in simulation be lowered to 0.1. The study shows that volatilization of TCE can be significant and volatilization losses should be taken into account when anaerobic activity in in-situ bioremediation applications is stimulated via addition of growth substrates. An implication of the modeling simulations is that maintaining a lower, but uniform, substrate concentration over the contaminated region may lead to faster contaminant degradation.     

Biotransformation and antioxidant response in Ceratophyllum demersum experimentally exposed to 1,2- and 1,4-dichlorobenzene

We report the effects of 1,2- and 1,4-dichlorobenzene (1,2-DCB and 1,4-DCB) on the aquatic macrophyte Ceratophyllum demersum. We evaluated the response of the antioxidant system through the assay of glutathione reductase (GR), guaiacol peroxidase (POD) and glutathione peroxidase (GPx). Additionally, the effect of DCBs on the detoxication system by measuring the activity of glutathione-S-transferase (GST) was evaluated.

C. demersum showed elevated GST activities when exposed to 10 and 20 mg l⁻¹ 1,2-DCB, and at 10 mg l⁻¹ for 1,4-DCB. These results show that glutathione conjugation take place at relatively high concentrations of both isomers. Significantly increased activities of POD were also detected in C. demersum exposed to concentrations above 5 mg l⁻¹ of the corresponding isomer.

The GR activity was enhanced in plants exposed to 1,2-DCB (5 mg l⁻¹) and 1,4-DCB (10 mg l⁻¹). GPx was also significantly increased in exposures to the corresponding isomer, each at a concentration of 10 mg l⁻¹. However, plants exposed to low doses of 1,4-DCB (1 mg l⁻¹) showed significantly decreased activities of both enzymes GR and GPx.

Consequently, it is clear that the exposure of the aquatic macrophyte C. demersum to DCBs is able to cause an activation of the antioxidant system, showing an isomer specific pattern, which suggests that the defence system of this plant is playing an important role in scavenging ROS, helping to protect the organism against adverse oxidative effects generated by the prooxidant action of the tested xenobiotics. Furthermore, increased GST activities give indirect evidence on the conjugation of either DCBs or the corresponding metabolites during phase II of detoxication, which supports the elimination process of toxic metabolites from cells of C. demersum.     

T-RFLP detection of nitrifying bacteria in a fluidized bed reactor of achieving simultaneous nitrification-denitrification

Steady simultaneous nitrification-denitrification (SND) was achieved in a fluidized bed reactor (FBR) by the control of DO concentration without physical separation of the aerobic and anoxic zones. The performance and composition of nitrifying bacteria were examined in this study. The ammonium removal efficiency was higher than 80% and the DO concentration (1-5 mg l(-1)) had little influence on it. More than 50% total nitrogen (TN) removal efficiency was achieved when DO was less than 3 mg l(-1) and in many cases the removal efficiency varied between 60-70%. The volumetric loading of TN varied between 0.12 and 0.20 kg Nm(-3)d(-1). 16S rRNA-based terminal restriction fragment length polymorphism analysis was used to characterize the diversity and distribution of the ammonia oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB) in the FBR. The results indicated that, the composition and number of both AOB and NOB changed with position in the reactor and operating time. Nitrosomonas sp. was found to be dominant species of the AOB community, and Nitrobacter sp. also existed in the system. The SND mechanism in the FBR was proved to be the vertical stratification of active populations; however, the presence of microenvironments within the biofilm cannot be ruled out.     

Alginate immobilized enrichment culture for atrazine degradation in soil and water system

An atrazine degrading enrichment culture, a consortium of bacteria of genus Bacillus along with Pseudomonas and Burkholderia, was immobilized in sodium alginate and was used to study atrazine degradation in mineral salts medium (MSM), soil and wastewater effluent. Sodium alginate immobilized consortium, when stored at room temperature (24 ± 5°C), was effective in degrading atrazine in MSM up to 90 days of storage. The survival of bacteria in alginate beads, based on colony formation unit (CFU) counts, suggested survival up to 90 days and population counts decreased to 1/5^th on 120 days. Comparison of atrazine degrading ability of the freely suspended enrichment culture and immobilized culture suggested that the immobilized culture took longer time for complete degradation of atrazine as a lag phase of 2 days was observed in the MSM inoculated with alginate immobilized culture. The free cells resulted in complete degradation of atrazine within 6 days, while immobilized cells took 10 days for 100% atrazine degradation. Further, immobilized cultures were able to degrade atrazine in soil and wastewater effluent. Alginate beads were stable and effective in degrading atrazine till 3rd transfer and disintegrated thereafter. The study suggested that immobilized enrichment culture, due to its better storage and application, can be used to degrade atrazine in soil water system.     

Nitrogen trace gas emissions from a riparian ecosystem in southern Appalachia

In this paper, we present two years of seasonal nitric oxide (NO), ammonia (NH₃), and nitrous oxide (N₂O) trace gas fluxes measured in a recovering riparian zone with cattle excluded and adjacent riparian zone grazed by cattle. In the recovering riparian zone, average NO, NH₃, and N₂O fluxes were 5.8, 2.0, and 76.7 ng N m⁻² s⁻¹ (1.83, 0.63, and 24.19 kg N ha⁻¹ y⁻¹), respectively. Fluxes in the grazed riparian zone were larger, especially for NO and NH₃, measuring 9.1, 4.3, and 77.6 ng N m⁻² s⁻¹ (2.87, 1.35, and 24.50 kg N ha⁻¹ y⁻¹) for NO, NH₃, and N₂O, respectively. On average, N₂O accounted for greater than 85% of total trace gas flux in both the recovering and grazed riparian zones, though N₂O fluxes were highly variable temporally. In the recovering riparian zone, variability in seasonal average fluxes was explained by variability in soil nitrogen (N) concentrations. Nitric oxide flux was positively correlated with soil ammonium (NH₄⁺) concentration, while N₂O flux was positively correlated with soil nitrate (NO₃⁻) concentration. Ammonia flux was positively correlated with the ratio of NH₄⁺ to NO₃⁻. In the grazed riparian zone, average NH₃ and N₂O fluxes were not correlated with soil temperature, N concentrations, or moisture. This was likely due to high variability in soil microsite conditions related to cattle effects such as compaction and N input. Nitric oxide flux in the grazed riparian zone was positively correlated with soil temperature and NO₃⁻ concentration. Restoration appeared to significantly affect NO flux, which increased ≈600% during the first year following restoration and decreased during the second year to levels encountered at the onset of restoration. By comparing the ratio of total trace gas flux to soil N concentration, we show that the restored riparian zone is likely more efficient than the grazed riparian zone at diverting upper-soil N from the receiving stream to the atmosphere. This is likely due to the recovery of microbiological communities following changes in soil physical characteristics.     

生物沸石球强化吸附氨氮废水的动力学研究

用一种具有多孔结构特征的沸石球作为载体固定化硝化细菌强化吸附氨氮废水。结果表明,沸石球能快速固定化硝化细菌,吸附动力学表明150 min对氨氮吸附容量达到2.816 mg/g,而且还有继续增加的趋势。假二级动力学方程和Elovich模型的精确拟合说明,生物沸石球对氨氮的吸附过程可能是非均相扩散起作用及以化学吸附反应为主的复杂转化过程。扩散拟合结果表明,氨氮在生物沸石球的吸附是以液膜扩散和颗粒内扩散为吸附速率的控制步骤,活性的硝化细菌对氨氮的硝化使氨氮在微孔的吸附得到了强化。     

Relationship between the loading rate of inorganic mercury to aquatic ecosystems and dissolved gaseous mercury production and evasion

The purpose of our study was to test the hypothesis that dissolved gaseous mercury (DGM) production and evasion is directly proportional to the loading rate of inorganic mercury [Hg(II)] to aquatic ecosystems. We simulated different rates of atmospheric mercury deposition in 10-m diameter mesocosms in a boreal lake by adding multiple additions of Hg(II) enriched with a stable mercury isotope (²⁰²Hg). We measured DGM concentrations in surface waters and estimated evasion rates using the thin-film gas exchange model and mass transfer coefficients derived from sulfur hexafluoride (SF₆) additions. The additions of Hg(II) stimulated DGM production, indicating that newly added Hg(II) was highly reactive. Concentrations of DGM derived from the experimental Hg(II) additions (“spike DGM”) were directly proportional to the rate of Hg(II) loading to the mesocosms. Spike DGM concentrations averaged 0.15, 0.48 and 0.94 ng l⁻¹ in mesocosms loaded at 7.1, 14.2, and 35.5 μg Hg m⁻² yr⁻¹, respectively. The evasion rates of spike DGM from these mesocosms averaged 4.2, 17.2, and 22.3 ng m⁻² h⁻¹, respectively. The percentage of Hg(II) added to the mesocosms that was lost to the atmosphere was substantial (33–59% over 8 weeks) and was unrelated to the rate of Hg(II) loading. We conclude that changes in atmospheric mercury deposition to aquatic ecosystems will not change the relative proportion of mercury recycled to the atmosphere.     

Direct measurement of denitrification activity in a Gulf coast freshwater marsh receiving diverted Mississippi River water

Wetland loss along the Louisiana Gulf coast and excessive nitrate loading into the Gulf of Mexico are interrelated environmental problems. Nitrate removal by soil denitrification activity was studied in a ponded freshwater marsh receiving diverted Mississippi River water for the purpose of reversing or slowing wetland loss. Labeled ¹⁵N-nitrate was applied at 3.8 g N m⁻² into four replicate study plots after removing above ground vegetation. Nitrogen gas (N₂) and nitrous oxide (N₂O) emissions from the plots were determined by isotope ratio mass spectrometry (IRMS). Nitrous oxide emissions were also compared with the results determined by gas chromatograph (GC). Results showed that it took 2 weeks to remove the added nitrate with N₂O emission occurring over a period of 4 d. The apparent denitrification dynamics were assumed to follow the Michaelis–Menten equation. The maximum denitrification rate and K_m value were determined as 12.6 mg N m ⁻² h⁻¹, and 6.5 mg N l⁻¹, respectively. Therefore the maximum capacity for nitrate removal by the marsh soil would be equivalent to 110 g N m⁻² yr⁻¹, with more than 30% of nitrogen gas evolved as N₂O. For typical nitrate concentrations in Mississippi River water of about 1 mg N l⁻¹, nitrate would be removed at a rate of 14.7 g N m⁻² yr⁻¹ with N₂O emission about 1.5%. A denitrification dynamic model showed that the efficiency of nitrate removal would largely depend on the water discharge rate into the ponded wetland. Higher discharge rate will result in less retention time for the water in the marsh where nitrate is denitrified.     

Feasibility of phosphate fertilizer to immobilize cadmium in a field

To reduce effectively cadmium (Cd) phytoextractability by phosphate fertilizer in Cd contaminated soil, fused and superphosphate (FSP) was applied at the rate of 0, 33.5 (recommendation level), 167.5, and 335 kg P ha⁻¹ for radish (Raphanus sativa L.). Unlike from what we expected, soil Cd extractability and Cd concentration in radish increased with increasing FSP application in the field. To determine the effect of FSP on Cd immobilization, FSP was mixed with the selected soil at the rate of 0, 200, 400, 800, and 1600 mg P kg⁻¹ and then incubated for 8 weeks. As observed in the field study, NH₄OAc extractable Cd concentration increased slightly with FSP addition up to 400 mg P kg⁻¹ and thereafter dramatically decreased upon increasing its application rate. Soil pH and negative charge were decreased at low level of FSP application up to 400 mg P kg⁻¹, but thereafter continually increased with increasing application level. This could be indirect evidence that net soil negative charge was increased by the specific adsorption of phosphate at the high rate of FSP application over 400 mg P kg⁻¹. The labile Cd fraction (water soluble and exchangeable + acidic fraction) increased with increasing FSP application by 400 mg P kg⁻¹ and thereafter gradually decreased with corresponding increase in unlabile fraction (oxidizable and residual fraction). Based on these results, FSP might be applied with a very high rate over 800 mg P kg⁻¹ to decrease Cd extractability in the selected field. However, this level is equivalent to 1440 kg P ha⁻¹, which is about 43 times higher than the recommendation levels for radish production and resulted in a significant increase in water soluble P concentration creating a new environmental problem. Therefore, the feasibility of FSP to reduce Cd extractability in the field is very low.     

A chemostat system for investigating pesticide biodegradation in continuous mixed bacteria cultures originating from surface water

To be able to predict the degradation (rate) of organic chemicals (e.g. pesticides) in the field, knowledge of the environmental conditions that are of influence on the degradation process are of importance. In the present study an experimental system is described which is used to study the degradation of organic pollutants in mixed bacteria cultures originating from surface water. With this system the degradation of compounds can be followed for relatively long experimental periods (months). In addition, it is possible to vary different environmental parameters in order to investigate their influences on the degradation of the chemical. These preliminary experiments show that growth and ‘composition’ of the bacteria culture have comparable patterns in parallel experiments. The first order degradation rate constant for the test compound dichloran, as calculated from these experiments under these circumstances, is about 0.002 h⁻¹.     

Effects of dissolved oxygen and iron aging on the reduction of trichloronitromethane, trichloracetonitrile, and trichloropropanone

Iron metal (Fe(0)) is a potent reductant capable of reducing a wide variety of halogenated organic compounds including disinfection byproducts (DBPs). These reduction reactions may play a role in DBP fate in iron water mains and potentially could be exploited to remove DBPs from drinking water or wastewater in a packed-bed configuration. Oxidants (i.e., dissolved oxygen (DO) and chlorine) present in the water, however, may decrease the DBP degradation rate by competing for reactive sites and rapidly aging or corroding the iron surface. Thus, batch experiments were performed to investigate the effect of DO on the degradation rates of selected DBPs by Fe(0). Experiments were performed under anaerobic conditions, in initially oxygen saturated buffer without DO control, and under controlled DO (approximately 4.0 or 8.0 mg l⁻¹) conditions. The effect of short-term (25–105 min) iron aging in DO-containing buffer on DBP degradation rate also was investigated in separate experiments. For fresh Fe(0), the degradation rates of trichloronitromethane (TCNM) and trichloroacetonitrile (TCAN) in initially oxygen saturated buffer were similar to their respective rates under anaerobic conditions. The degradation rate of 1,1,1-trichloropropanone (1,1,1-TCP), however, decreased significantly in the presence of DO and the effect was proportional to DO concentration in the controlled DO experiments. For a DO concentration of 4 mg l⁻¹, the degradation rate of the three DBPs was greater for longer aging times as compared to their respective rates after 25 min, suggesting the formation of a mineral phase that increased reactivity. For a DO concentration of 8 mg l⁻¹, the effects of increasing aging time were mixed. TCNM degradation rates were stable for all aging times and comparable to that under anaerobic conditions. The TCAN and 1,1,1-TCP degradation rates, however, tended to decrease with increasing aging time. These results suggest that the reduction of highly reactive DBPs by Fe(0) will not be affected by the presence of DO but that the reaction rates will be slowed by DO for DBPs with slower degradation kinetics.     

Methane fluxes from tundra soils and snowpack in the maritime Antarctic

Methane fluxes were measured from three exposed tundra sites and four snowpack sites on the Fildes Peninsula in the maritime Antarctic in the summertime of 2002. The average fluxes at two normal tundra sites were −15.3 μg m⁻² h⁻¹ and −14.3 μg m⁻² h⁻¹, respectively. The fluxes from tundra site with fresh penguin dropping addition showed positive values with the average of 36.1 μg m⁻² h⁻¹, suggesting that the deposition of fresh droppings greatly enhanced CH₄ emissions from the poor Antarctic tundra during penguin breeding periods. The summertime variation in CH₄ flux was correlated with surface ground temperature and the precipitation. The correlation between the flux and PT₀, which is the product of the precipitation and surface ground temperature, was quite strong. The diurnal cycle of CH₄ flux from the tundra soils was not obtained due to local fluky weather conditions. The fluxes through four snowpack sites were also obtained by the vertical CH₄ concentration gradient and their average fluxes were −46.5 μg m⁻² h⁻¹, −28.2 μg m⁻² h⁻¹, −46.4 μg m⁻² h⁻¹ and −17.9 μg m⁻² h⁻¹, respectively, indicating that tundra soils under snowpack also consume atmospheric CH₄ in the maritime Antarctic; therefore these fluxes could constitute an important part of the annual CH₄ budget for Antarctic tundra ecosystem.     

The use of physiological characteristics for comparison of organic compounds phytotoxicity

The influence of intact (FLT) and photomodified (phFLT) fluoranthene (0.05, 0.5 and 5 μmol l⁻¹) and herbicide Basagran (5, 20, 35 and 50 nmol l⁻¹) on the germination, growth of seedlings and photosynthetic processes in pea plants (Pisum sativum L., cv. Garde) was investigated. The germination was significantly inhibited already by the lowest concentration (0.05 μmol l⁻¹) of FLT and phFLT, while Basagran caused inhibition only in higher concentrations (35 and 50 nmol l⁻¹). The growth of roots was significantly inhibited by higher concentration 5 μmol l⁻¹ of both FLT and phFLT and the shoot of seedlings was significantly influenced only by photomodified form. The length of root and shoot was inhibited already by concentration 5 nmol l⁻¹ of Basagran. Organic compounds applied on chloroplasts suspension influenced primary photochemical processes of photosynthesis. In chlorophyll fluorescence parameters, the significant increase of F₀ values and the decrease of F_V/F_M and Φ_II values by application of FLT (0.5 and 5 μmol l⁻¹) and phFLT (0.05, 0.5 and 5 μmol l⁻¹) was recorded. The maximum capacity of PSII (F_V/F_M) was influenced by the highest (50 nmol l⁻¹) and the effective quantum yield of PSII (Φ_II) already by the lowest (5 nmol l⁻¹) concentration of Basagran. Hill reaction activity decreased and was significantly inhibited by higher concentration (0.5 and 5 μmol l⁻¹) of FLT and phFLT and already by the lowest concentration (5 nmol l⁻¹) of Basagran.     

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.