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PubMed2003

Application of advanced oxidation processes to different industrial wastewaters.

This study examines the application of photochemical and non-photochemical advanced oxidation processes on the treatment of textile, Kraft bleaching, photoprocessing, and pharmaceutical wastewaters. Effects of reaction conditions on the treatment efficiency of industrial wastewater have been investigated. The results were evaluated in terms of biodegradability enhancement. The results indicated depending upon the composition of wastewater and applied pretreatment all applied AOPs had an ability to increase the biodegradability of studied wastewaters.

Biodegradation, Environmental↗
PubMed2005

Application of Box-Wilson experimental design method for the photodegradation of bakery's yeast industry with UV/H2O2 and UV/H2O2/Fe(II) process.

Decolorization and mineralization of bakery's yeast industry effluent by photochemical advanced oxidation processes (AOPs) utilizing UV with hydrogen peroxide and Photo-Fenton, were investigated in a laboratory scale photo-reactor equipped with a 16 W low-pressure mercury vapor lamp. The Box-Wilson experimental design method was employed to evaluate the effects of major process variables (e.g. pH, oxidant dose, and irradiation time) on the decolorization efficiency. Response function coefficients were determined by regression analysis of the experimental data and prediction results agreed with the experimental results. The optimum hydrogen peroxide concentration and irradiation time were found to be 5 mM and 50 min at pH 3, respectively, for UV/H2O2 process. In the Photo-Fenton process application, maximum decolorization efficiency (96.4%) was obtained at the optimum reaction conditions that were 100 mM H2O2 and 1 mM Fe(II) doses at pH 3, and 10 min of irradiation time.

Ferric Compounds↗
PubMedDate not supplied

Ultraviolet corneal photoablation.

PURPOSE: The purpose of this article is to discuss missing information on the basic physical and biological processes of ultraviolet corneal photoablation and to evaluate its potential clinical implications. METHODS: A physical description of ultraviolet laser corneal ablation that includes photothermal, photochemical, and radiative processes is proposed. RESULTS: Unresolved issues include the nature of the primary ablation process, the tissue and biological effects of the photothermal and photochemical components of the interaction, and the static and dynamic absorption process. CONCLUSIONS: A better understanding of the basic physics and biology of ultraviolet corneal photoablation may help us better understand, predict, and perhaps minimize the effect of tissue hydration, plume formation, and other factors that affect the predictability of ablation and the induced tissue damage.

Cornea↗
PubMed2005

Multiple roles of a conserved GAF domain tyrosine residue in cyanobacterial and plant phytochromes.

The phytochrome family of red/far-red photoreceptors has been optimized to support photochemical isomerization of a bound bilin chromophore, a process that triggers a conformational change and modulates biochemical output from the surrounding protein scaffold. Recent studies have established that the efficiency of this photochemical process is profoundly altered by mutation of a conserved tyrosine residue (Tyr176) within the bilin-binding GAF domain of the cyanobacterial phytochrome Cph1 [Fischer, A. J., and Lagarias, J. C. (2004) Harnessing phytochrome's glowing potential, Proc. Natl. Acad. Sci. U.S.A. 101, 17334-17339]. Here, we show that the equivalent mutation in plant phytochromes behaves similarly, indicating that the function of this tyrosine in the primary photochemical mechanism is conserved. Saturation mutagenesis of Tyr176 in Cph1 establishes that no other residue can support comparably efficient photoisomerization. The spectroscopic consequences of Tyr176 mutations also reveal that Tyr176 regulates the conversion of the porphyrin-like conformation of the bilin precursor to a more extended conformation. The porphyrin-binding ability of the Tyr176Arg mutant protein indicates that Tyr176 also regulates the ligand-binding specificity of apophytochrome. On the basis of the hydrogen-bonding ability of Tyr176 substitutions that support the nonphotochemical C15-Z,syn to C15-Z,anti interconversion, we propose that Tyr176 orients the carboxyl side chain of a conserved acidic residue to stabilize protonation of the bilin chromophore. A homology model of the GAF domain of Cph1 predicts a C5-Z,syn, C10-Z,syn, C15-Z,anti configuration for the chromophore and implicates Glu189 as the proposed acidic residue stabilizing the extended conformation, an interpretation consistent with site-directed mutagenesis of this conserved acidic residue.

Amino Acid Substitution↗
PubMed2003

Long-term variation in surface ozone and its precursors in Athens, Greece: a forecasting tool.

INTENTION, GOAL, SCOPE, BACKGROUND: Photochemical pollution is a very complex process involving meteorological, topographic, emission and chemical parameters. The most important chemical mechanisms involved in the atmospheric process have already been identified and studied. However, many unknown parameters still exist because of the large number of participating chemical reactions. OBJECTIVE: The present study investigates the processes involved in the photochemical pollution effect of an urban station located in the greater area of the Athens basin and gives a plausible explanation for the different seasonal ozone development between that station and another rural one. Furthermore, the distribution of the mean monthly surface ozone observed at the urban station during 1987-2001 is examined in order to create a relevant forecasting tool. METHODS: Averaged hourly data of O3 and NOx observations monitored at the above mentioned stations, during 1987-2001, have been used in order to derive the daytime (7:00-15:00) values. Trajectories calculated by using a 2D-trajectory code and meteorological data, during the period 1988-1996, have also been used. RESULTS AND DISCUSSION: At the urban station, the percentage negative trend of NO and NOx data in winter and summer is higher than that in spring and autumn, while the percentage ozone trend is maximum in the summer. On the contrary, the negative surface ozone trend at the rural station exhibits a minimum in summer and a maximum in autumn and winter. The mean seasonal wind-rose for the selected months shows that the northward wind flow dominates during June, the month of the lowest negative ozone trend in the rural station. Finally, the development of the forecasting tool shows that the mean monthly surface ozone data during the period (1987-2001) demonstrates a semi-log distribution. CONCLUSIONS: Air transport effect on the air pollution of the rural station (not blocked by mountains) is deduced as a possible reason for the different seasonal ozone development observed between the rural and the urban station. Finally, the discrepancies between the theoretical probabilities deduced by the model and the empirical ones appear to be very small, and the corresponding correlation coefficient is 0.99. RECOMMENDATION AND OUTLOOK: However, to interpret the aforementioned statistical results about the negative trends in ozone and its precursors, additional parameters can be taken into account. Changes in NOx concentrations, for instance, can result not only from changes in emissions or meteorological conditions. There might also be a contribution through changes in the atmospheric composition. A study of the contribution of changes in atmospheric composition to trends of observed NOx concentrations requires that a series of steps be taken (removal of meteorological influence in the time series, calculation of trends in OH concentrations, etc.).

Air Movements↗
PubMed2004

Functional characteristics of photochemically treated platelets.

BACKGROUND: A photochemical treatment (PCT) process using the psoralen compound amotosalen HCL (S59) and long wavelength UVA light was developed for inactivation of infectious pathogens and WBCs. In this study the effect of PCT on functional characteristics of the platelets was evaluated in vitro. STUDY DESIGN AND METHODS: Platelet concentrates were treated photochemically using the experimental clinical processing system T-bag S59 Reduction Device (SRD) (n = 4) or the commercially available integral processing system Wafer SRD (n = 4) and compared with control platelet concentrates in plasma/PAS III alone (n = 4). The evaluation included variables with respect to the overall quality of the product (e.g., HSR, pH), the function (aggregation and activation tests), apoptosis (annexin V and caspase 3), and lysis. RESULTS: No differences were found in the product quality variables, in P-selectin expression, and the apoptosis variables. PCT using the T-bag SRD led to a significant decrease in aggregation capacity with collagen and thrombin and a significant increase in plasma LDH, whereas no differences for the Wafer SRD were found. CONCLUSION: PCT using the experimental T-bag SRD led to a significant decrease in platelet function. However, the commercially available Wafer SRD had only minor in vitro effects on the quality of the platelets.

Apoptosis↗
PubMed2004

Integration of advanced oxidation technologies and biological processes: recent developments, trends, and advances.

The greatest challenge of today's wastewater treatment technology is to optimize the use of biological and chemical wastewater treatment processes. The choice of the process and/or integration of the processes depend strongly on the wastewater characteristics, concentrations, and the desired efficiencies. It has been observed by many investigators that the coupling of a bioreactor and advanced oxidation processes (AOPs) could reduce the final concentrations of the effluent to the desired values. However, optimizing the total cost of the treatment is a challenge, as AOPs are much more expensive than biological processes alone. Therefore, an appropriate design should not only consider the ability of this coupling to reduce the concentration of organic pollutants, but also try to obtain the desired results in a cost effective process. To consider the total cost of the treatment, the residence time in biological and photochemical reactors, the kinetic rates, and the capital and operating costs of the reactors play significant roles. In this study, recent developments and trends (1996-2003) on the integration of photochemical and biological processes for the degradation of problematic pollutants in wastewater have been reviewed. The conditions to get the optimum results from this integration have also been considered. In most of the studies, it has been shown that the integrated processes were more efficient than individual processes. However, slight changes in the configuration of the reactors, temperature, pH, treatment time, concentration of the oxidants, and microorganism's colonies could lead to a great deviation in results. It has also been demonstrated that the treatment cost in both reactors is a function of time, which changes by the flow rate. The minimum cost in the coupling of the processes cannot be achieved unless considering the best treatment time in chemical and biological reactors individually.

Bioreactors↗
PubMedDate not supplied

Intracellular kinetics of ATX-S10.Na(II) and its correlation with photochemical reaction dynamics during a pulsed photosensitization process: effect of pulse repetition rate.

Although photodynamic therapy with pulsed light excitation has interesting characteristics, its photosensitization mechanism has not been fully elucidated. In this study, we showed that the intracellular kinetics of ATX-S10.Na(II), a lysosomal sensitizer, was closely related to photochemical reaction dynamics during photodynamic treatment of A549 cells with nanosecond pulsed light. Fluorescence microscopy revealed that at high frequencies of 10 and 30 Hz the sensitizer initially localized mainly in lysosomes but that it started to be redistributed to the cytosol in certain ranges of radiant exposures. These ranges were found to coincide with a regime of fluorescence degradation with limited oxygen consumption. On the other hand, at 5 Hz, there was no such a discontinuous behavior in the sensitizer redistribution characteristics throughout the period of irradiation; this was consistent with the fact that no reaction switching was observed. Two possible reasons for the appearance of the regime with limited oxygen consumption are discussed: participation of an oxygen-independent reaction and change in the microenvironment for the sensitizer caused by lysosomal photodamage. The pulse frequency-dependent intracellular kinetics of the sensitizer also explains our previous results showing higher cytotoxicity at 5 Hz than at 10 and 30 Hz.

Adenocarcinoma↗
PubMed2001

Pharmacokinetic and toxicology assessment of INTERCEPT (S-59 and UVA treated) platelets.

The pathogen inactivation process developed by Cerus and Baxter Healthcare Corporations uses the psoralen, S-59 (amotosalen) in an ex vivo photochemical treatment (PCT) process to inactivate viruses, bacteria, protozoans, and leukocytes in platelet concentrates and plasma. Studies were performed by intravenous infusion of S-59 PCT formulations +/- compound adsorption device (CAD) treatment and with non-UVA illuminated S-59, using doses that were multiples of potential clinical exposures. The studies comprised full pharmacokinetic, single- and repeated-dose (up to 13 weeks duration) toxicity, safety pharmacology (CNS, renal, and cardiovascular), reproductive toxicity, genotoxicity, carcinogenicity testing in the p53(+/-) mouse, vein irritation, and phototoxicity. No specific target organ toxicity (clinical or histopathological), reproductive toxicity, or carcinogenicity was observed. S-59 and/or PCT formulations demonstrated CNS, ECG, and phototoxicity only at supraclinical doses. Based on the extremely large safety margins (>30,000-fold expected clinical exposures), the CNS and ECG observations are not considered to have any toxicological relevance. Additionally, after a complete assessment, mutagenicity and phototoxicity results are not considered relevant for the proposed use of INTERCEPT platelets. Thus, the results of an extensive series of in vitro and in vivo studies have not demonstrated any toxicologically relevant effects of platelet concentrates prepared by the INTERCEPT system.

Animals↗
PubMed2000

Degradation and toxicity reduction of textile effluent by combined photocatalytic and ozonation processes.

To minimize the environmental impact of textile effluents, mainly related to their high coloration and the presence of toxic or carcinogenic reactive dyes, the efficiency of photochemical and ozonation processes, applied in the form of isolated and combined procedures, were evaluated. The investigation was focused on the reduction of total organic carbon content (TOC), color and acute toxicity (monitoring by inhibition of Escherichia coli respiration). For a reaction time of 60 min, the anatase TiO2-assisted photocatalytic process produces color and TOC reduction of about 90% and 50%, respectively. Meanwhile, the ozonation process gives a decolorization of about 60% but negligible TOC reduction. When the processes were applied in a simultaneous form, the decolorization was almost complete and the TOC reduction was higher than 60%. The three treatments studied yield an acute toxicity reduction of around 50%.

Biodegradation, Environmental↗
PubMed2006

Model applications and intermediates quantification of atrazine degradation by UV-enhanced fenton process.

Degradation of the herbicide atrazine (ATZ) by the UV-enhanced Fenton process (UV-FP) was investigated. An enhanced photochemical effect was observed in the process compared with the simple combination of the two individual reaction rates of sole-UV (UV radiation) and dark-FP (sole Fenton's process). Accordingly, a photochemical model based on the two parallel reactions was proposed to predict the reaction kinetics of UV-FP, where two rate enhancement factors were adopted and found to be capable of successfully describing the rate improvement. In addition, the transformation pathway of ATZ decay was successfully investigated by using novel technology, liquid chromatography-electrospray tandem mass spectrometry (LC/ESI-MS/MS). Fourteen intermediates were identified in the process. The alkylic oxidation followed by dealkylation and/or dechlorination-hydroxylation was found to be the major pathway of the decay of ATZ in UV-FP. All of the detected intermediates were found to be dealkylated in different levels or positions. The dealkylated species were found to be further dechlorinated. The chlorinated products reduced to 17% of total, whereas the dechlorinated products remained at 73% and were further decayed after 60 min of treatment. In view of the gradual reduction of the mass balance of the total s-triazine, this suggested that a ring cleavage may occur on the ATZ in the UV-FP.

Atrazine↗
PubMed2000

Changes in the xanthophyll cycle and fluorescence quenching indicate light-dependent early events in the action of paraquat and the mechanism of resistance to paraquat in Erigeron canadensis (L.) cronq.

Violaxanthin de-epoxidation, chlorophyll fluorescence quenching, and photosynthetic O(2) evolution in the presence of paraquat (Pq) were studied in intact attached leaves of Pq-susceptible, and Pq-resistant (PqR) biotypes of Erigeron canadensis under different light conditions. Initially, similar changes were induced in the two biotypes, but the effects relaxed only in the PqR plants, indicating a Pq elimination process. The penetration of Pq into the chloroplasts of PqR plants proved to be somewhat restricted and highly light-dependent, as revealed by both the light response curves of violaxanthin de-epoxidation and fluorescence quenching and the short-term high-light pre-illumination experiments. An irregular down-regulation of the non-photochemical fluorescence quenching processes was observed, reflected by lower steady-state zeaxanthin and non-photochemical fluorescence quenching levels as compared with the corresponding non-treated high-light controls. It is concluded that light is essential not only for the initiation of the mechanism of resistance to Pq, but also for the penetration of Pq into the chloroplasts in the PqR E. canadensis. Also, the Pq elimination process may cause a modification to the regulation of the non-radiative energy dissipation in PqR plants in the presence of Pq.

Fluorescence↗
PubMed2003

Photochemical electrocyclization of the indolinylphenylethenes involving a C-N bond formation.

[reaction: see text] A novel oxidative photodehydrocyclization of indolinylphenylethenes to a polycyclic heteroaromatic cation with good yields was described. Starting from the trans derivative, the phototransformation is a multistep process. The process includes two photochemical reactions and a trans-cis isomerization reaction, followed by an 1-aza-1,3,5-hexatrienic electrocyclic reaction involving the formation of a C-N bond. The cyclized product gives the stable heteroaromatic cations from hydride elimination with oxygen from air or iodine.

Journal Article↗
PubMed2006

Occurrence and fate of the cytostatic drugs cyclophosphamide and ifosfamide in wastewater and surface waters.

The two oxazaphosphorine compounds cyclophosphamide and ifosfamide are important cytostatic drugs used in the chemotherapy of cancer and in the treatment of autoimmune diseases. Their mechanism of action, involving metabolic activation and unspecific alkylation of nucleophilic compounds, accounts for genotoxic effects described in the literature and is reason for environmental concern. The occurrence and fate of cyclophosphamide and ifosfamide were studied in wastewater treatment plants (WWTPs) and surface waters in Switzerland, using a highly sensitive analytical method based on solid-phase extraction and liquid chromatography tandem mass spectrometry. The compounds were detected in untreated and treated wastewater at concentrations of <0.3-11 ng/L, which corresponded well with concentrations predicted from consumption data and typical renal excretion rates. Weekly loads determined in influent and effluent wastewater were comparable and suggested a high persistence in WWTPs. Furthermore, no degradation was observed in activated sludge incubation experiments within 24 h at concentrations of approximately 100 ng/L. Processes that may be relevant for elimination in natural waterbodies were studied with a set of incubation experiments in the laboratory. After extrapolation to natural conditions in surface waters, a slow dark-chemical degradation (half-lives on the order of years) is the most important transformation process. Degradation by photochemically formed HO* radicals may be of some relevance only in shallow, clear, and nitrate-rich waterbodies but could be further exploited for elimination of these compounds by advanced oxidation processes, i.e., in a treatment of hospital wastewater. In surface waters, concentrations ranged from < or =50 to 170 pg/L and were thus several orders of magnitude lower than the levels at which acute ecotoxicological effects have been reported in the literature (mg/L range). However, due to a lack of studies on chronic effects on aquatic organisms and data on occurrence and effects of metabolites, a final risk assessment cannot be made.

Chromatography, Liquid↗
PubMed2005

Coagulation factor levels in cryosupernatant prepared from plasma treated with amotosalen hydrochloride (S-59) and ultraviolet A light.

BACKGROUND: The standard treatment for thrombotic thrombocytopenic purpura (TTP) is plasma exchange with fresh-frozen plasma (FFP). Exposure to large volumes of FFP increases the risk of transfusion-transmitted infections. Cryosupernatant (CSP) offers a theoretical advantage over FFP, because it lacks the large von Willebrand factor (VWF) forms implicated in the pathogenesis of TTP. This study compared the hemostatic variables of CSP prepared from FFP treated with a photochemical pathogen inactivation process to CSP prepared from conventional FFP. STUDY DESIGN AND METHODS: Forty CSP units were prepared from North American blood group A donor FFP. Twenty-one of the FFP units were individually treated with amotosalen hydrochloride (S-59) and ultraviolet A light (test, photochemically treated FFP), and 19 units were not treated (control, FFP). RESULTS: Hemostatic variables of test and control CSP were similar and within reported ranges for conventional FFP with the exception of those properties depleted in CSP. VWF-cleaving protease activity (VWF:CP) and protein S (PS) levels (total and free antigen and activity) were within the conventional FFP reference range for test and control CSP. There were statistical differences between test and control CSP for alpha(2)-antiplasmin, antithrombin, protein C, and VWF:CP on a per-volume basis, but all levels were within the reference range for FFP, and the differences were not significant when expressed per gram of CSP protein. CONCLUSION: S-59-treated CSP retained adequate levels of critical plasma proteins for plasma exchange therapy in acute TTP. The data indicate good preservation of hemostasis control proteins such as PS, alpha(2)-antiplasmin, and VWF:CP activity (ADAMTS13).

Bacterial Infections↗
PubMed2003

Heterogeneous photochemical reactions of decabromodiphenyl ether.

Brominated diphenyl ethers are a major class of brominated flame retardants, with production of decabromodiphenyl ether (DBDPE) contributing significantly to this total. Although little is known about the mechanisms and rates of DBDPE decay in the natural environment, photochemical transformation is often suggested as a potentially important fate process. In this study, photochemical reactions of DBDPE precipitated onto hydrated surfaces (quartz glass, silica particles, and humic acid-coated silica particles) were measured. Decabromodiphenyl ether was irradiated within a Rayonet photochemical reactor equipped with lamps having maximum emissions (lambdamax) at 300 or 350 nm or with sunlight (West Lafayette, IN, USA at 40 degrees 26'N, 86 degrees 55'W). When DBDPE is plated onto quartz tubes and hydrated with reagent-grade water, phototransformation occurred over a period of days with each light source. With two lamps (lambdamax = 300 nm), about 31% of the initial mass of DBDPE remained after 60 h in the Rayonet reactor. Decabromodiphenyl ether transformed more slowly when irradiated by sunlight, with 30% of the initial compound recovered from tubes after 72 h. In the presence of humic acid (HA) solution, transformation of DBDPE by solar irradiation is slowed even further: approximately 70% remained after 72 h. Solar irradiation of DBDPE adsorbed to humic acid-coated sand particles resulted in the slowest irradiation rates; approximately 88% of the initial mass was recovered after 96 h of exposure. Although the parent compound exhibited slow transformation, analysis by high-performance liquid chromatography (HPLC) indicated some accumulation of transformation products.

Bromine↗
PubMed2004

Reversible optical transcription of supramolecular chirality into molecular chirality.

In nature, key molecular processes such as communication, replication, and enzyme catalysis all rely on a delicate balance between molecular and supramolecular chirality. Here we report the design, synthesis, and operation of a reversible, photoresponsive, self-assembling molecular system in which molecular and supramolecular chirality communicate. It shows exceptional stereoselectivity upon aggregation of the molecules during gel formation with the solvent. This chirality is locked by photochemical switching, a process that is subsequently used to induce an inverted chiral supramolecular assembly as revealed by circular dichroism spectroscopy. The optical switching between different chiral aggregated states and the interplay of molecular and supramolecular chirality offer attractive new prospects for the development of molecular memory systems and smart functional materials.

Journal Article↗