Charge density of total organic carbon in Finnish lakes

Ion balance calculations were used to estimate the charge density of total organic carbon (TOC) and for calibrating the model of Oliver et al. (1983) for Finnish lakes. The database consisted of samples collected in the autumn of 1987 from 955 randomly selected lakes covering the whole country. Organic anion concentrations were estimated as the difference between Sigma cations and Sigma inorganic anions. The charge density of TOC was estimated by dividing the organic anion concentration by TOC. The median charge density was 7.5 microeq (mg TOC)(-1). In lakes with pH values lower than 4.5 the average charge density was 5.2 microeq (mg TOC)(-1) and it increased to 10.3 microeq (mg TOC)(-1) in lakes with pH higher than or equal to 7.0. The calibrated model explained 79% of the observed variability in organic anion concentration. The value for the total amount of acidic functional groups per mol organic carbon in the model of Oliver et al. (1983) was slightly higher compared to the Finnish calibration. At pH values higher than 4.4 the Finnish calibration gives lower organic anion concentrations compared to the model of Oliver et al. (1983).     

Artificial acidification of a non-acidic and an acidic headwater stream in Maine, USA

Two headwater streams with low DOC and different pHs (4.5-4.8 and 5-6.5) were acidified with H2SO4 to pH 4.1 and 4.5, respectively, for 24-h periods. Neutralization of the added acid occurred by protonation of ANC (HCO3-dominated in the higher pH stream), desorption of Ca (< 15 microeq litre(-1)) and Mg (<6 microeq litre(-1)), and desorption and dissolution of AL (<250 microg litre(-1)) from the stream bed. The concentrations of dissolved organic carbon (DOC) remained constant within the experimental reaches. The concentrations of Na, K an H4SiO4 also remained constant, indicating no detectable increase in the rate of chemical weathering in the stream bed. After acid addition was stopped, concentrations of Ca, Mg and Al decreased to below background, indicating reversible ion exchange as the principal mechanism for the mobility of Ca and Mg and to a lesser extent for Al. Repeated acidifications indicated that significant regeneration of cations on the exchange surfaces of the stream substrate occurs rapidly.     

Recovery from acidification in central Europe--observed and predicted changes of soil and streamwater chemistry in the Lysina catchment,Czech Republic

The geochemical model MAGIC was applied to estimate streamwater and soil chemistry between 1851 and 2030 at the Lysina catchment, an acid-sensitive granitic catchment covered by planted Norway spruce monoculture in the western Czech Republic. The total deposition of sulfur to the catchment was 164 meq m(-2) in 1991, but had declined to 52 meq m(-2) by 2000. Although SO2 emissions in the region declined by 90% compared to the 1980s, acidification recovery was small within the period 1990-2000. Stream pH increased only slightly (from 3.92 to 4.07), although SO4 concentration declined sharply from 568 microeq l(-1) (1990) to 232 microeq l(-1) (2000). Organic acids played an important role in streamwater buffering. According to the MAGIC prediction using deposition measured in 1999-2000, streamwater pH will increase to 4.3 and soil base saturation will increase to 6.2% by 2030 (from 5.7% in 2002). Pre-industrial pH was estimated to be 5.5 and soil base saturation 24.7%. The loss of base cations (Ca, Mg, Na, K) was caused predominantly by atmospheric acidity, but intensive forestry was responsible for approximately one third of the net base cation loss via accumulation in harvested biomass. Severely damaged sites, under continued pressure from forestry, will not return to a good environmental status in the near future (if ever) when the acid deposition input is only partially reduced.     

AOX Formation and Elimination in the Oxidative Treatment of Synthetic Wastewaters in a UV-Free Surface Reactor (6 pp)

Intention, Goal, Scope, Background The effect of chloride concentration and pH on the UV oxidation systems was examined. Phenol and methanol were used as organic substances. The treatment of these chemicals by UV oxidation using a newly developed lab scale pretest UV-Free Surface Reactor (UV-FSR) with and without Cl– addition at different pH values, is evaluated. Results of this study indicated that the Cl– concentration of the water and the chemical structure of the substances is more important than the pH of the water. There was no AOX at the beginning of the experiments, but a de-novo synthesis of AOX was observed during the batch experiments. This is caused by the high chloride content of the wastewaters. It can be supposed that OHradicals oxidize some chloride-ions to form chlorine, which further reacts with organic compounds. During the treatment, these AOX compounds which are produced from the beginning of the reaction are destroyed again. Evaluations of these experiments were done according to TOC and AOX results. Approximately 80% and 99% TOC removal efficiencies were obtained for the treatment of Phenol and Methanol-containing wastewaters, respectively. Objective In the literature, there are no relevant publications concerning the AOX formation of wastewater by wet oxidation- iron catalysed or by application of UV. For that reason, the main objectives of this study were: 1. to see the influence of chloride concentration and pH on the AOXde-novo formation with newly developed UV-Free Surface Reactor (UV-FSR), 2. to make a comparison of different AOPs, 3. to observe the effect of the chloride concentration on the TOC degradation efficiency, 4. to optimise reaction conditions. Methods In synthetic wastewaters, Methanol (CH3OH) and Phenol (C6H5 OH) are used as pollutants. The concentration of each substance was 1000 mg/l and COD values were calculated theoretically. The H2O2 addition was calculated according to the COD with a convenient stoichiometric factor (e.g. 1). During experiments, the pH was always kept constant with the addition of either 25% H2SO4 or 33% NaOH depending on the experimental conditions. Each substance was treated with the addition of 1000 mg/l Cl–, 10000 mg/l Cl– and without Cl– addition at pH 3, pH 7 and pH 10, respectively. NaCl was used as a Cl– source. Adsorbable Organic Halogenides (AOX) were determined using a TOX analyser (European Standard EN 1485 H 14, 1996). TOC measurements were carried out using an Elementar High TOC Analyzer equipped with an auto sampler. The H2O2 concentration was measured according to German Standard Methods (DIN 38409, Part 15, 1987). Results and Discussion The first step was to determine the effect of pH on the AOX formation in the process. Therefore, experiments were carried out at three different pHs: acidic (pH 3), neutral (pH 7) and basic (pH 10) conditions at a constant initial Methanol concentration of 1000 mg/l and a hydrogen peroxide concentration of 3185 mg/l (1 x stoichiometric). All results were evaluated according to applied pH. At these conditions, the amount of H2O2 (53 ml / 10 l) concentration was nearly zero after 1 hour batch treatment of Methanol. There was no AOX at the beginning of the experiments, but the AOX value increased after 6–18 min. At the end of 1 hour batch treatment this produced AOX was treated again. The maximum AOX production was obtained with the addition of 10000 mg/l Cl–, whereas there is no AOX production during the experiment when Cl– was not used. In all studies, however, TOC values decreased to almost zero after 1 hour batch treatment. After the experiments with Methanol, Phenol treatment was carried out at different pHs as a second experiment. pH was kept constant with the addition of either H2SO4 or NaOH depending on the experimental conditions. During experiments with Phenol, the colour of the water changed from colourless to a yellowish- red. After 1 hour treatment, the colour of the water was red. Therefore, these experiments were continued until the water became colourless again, and this took about 5 hours. Although there was no AOX at the beginning of the experiments, it increased after 30 min to 1 hour oxidation with the addition of 1000 mg/l Cl– and 10000 mg/l Cl–. There was no AOX production during the experiments when Cl– was not added. At the end of 5 hours of treatment, formed AOX was degraded and the TOC concentration decreased from 766 mg/l to approximately 200 mg/l. Conclusion. These experiments of this study showed that the effects of Cl– concentration of the water and the chemical structure of the substances is more than that of the pH on the AOX formation. During the batch experiments, a de-novo synthesis of AOX was observed very impressively due to the high chloride content of the wastewaters. It can be implied that OH-radicals oxidize some chloride-ions to form chlorine, which further reacts with organic compounds so that AOXde-novo is formed. At the end of the reaction times these AOX compounds are also destroyed. Recommendation and Outlook It is more cost effective to use these processes for only purposes such as toxicity reduction, enhancement of biodegradability, decolourisation and removal of micropollutants. However, the most important point is the optimization of the reaction conditions for the process of concern. The AOP applied can be used, for instance, for AOX reduction and TOC removal of industrial wastewaters.     

Role of cupric ions in the H2O2/UV oxidation of humic acids

The purpose of this study is to reveal the role of cupric ions as a natural water contaminant in the H2O2/UV oxidation of humic acids. Humic acids are naturally occurring organic matter and exhibit a strong tendency of complexation with some transition metal ions. Chlorination of humic acids causes potential health hazards due to formation of trihalomethane (THM). The removal of THM precursors has become an issue of public concern. The H2O2/UV process is capable of mineralizing humic acids due to formation of a strong oxidant, hydroxyl radicals, in reaction solution. Experiments were conducted in a re-circulated photoreactor. Different cupric concentrations (0-3.8 mg/l) and different pH values (4-9) were controlled to determine their effects on the degradation of humic acids, UV light absorbance at 254 nm, and H2O2. The presence of cupric ions inhibits humic mineralization and decreases the rate of destruction of humic acids which absorb UV light at 254 nm. On the other hand, the higher the cupric concentration, the lower the H2O2 decomposition rate. In the studied pH range, the minimum of total organic carbon (TOC) removal occurs at pH = 6 in the presence of 2.6 mg/l of cupric ions; both acidification (pH = 4) and alkaline condition (pH = 9) lead to a better removal of TOC. It is inferred from this study that the cupric-complexed form of humic acids is more refractory than the non-complexed one.     

The MAGIC simulation of surface water acidification at, and first year results from, the Bear Brook Watershed Manipulation, Maine, USA

The catchments of East and West Bear Brooks, Maine, USA, have been hydrologically and chemically monitored for 3.5 years. Stream chemistries and hydrographs are similar. These clear water streams are low in ANC (0-70 microeq litre(-1)), with variations caused by changing concentrations of base cations, SO4, NO3 and Cl. The latter range between 90-120, 0-40 and 65-75 microeq litre(-1), respectively. The West Bear catchment is being treated with six applications per year of dry (NH4)2SO4 at 1800 eq ha(-1) year(-1). After one year of treatment, the response of the stream chemistry and the response modelled by MAGIC are similar. Retentions of NH4 and SO4 are nearly 100% and greater than 80%, respectively. The additional flux of SO4 is compensated principally by an increased Ca concentration. Episodes of high discharge in the treated catchment are now characterized by lower ANC and pH, and higher Al than prior to the manipulation. Concentrations of NO3 have increased about 10 microeq litre(-1) during the dormant season, presumably due to additional nitrification of N from NH4. Discharge-chemistry relationships indicate that changes in stream chemistry, except for NO3, are dominated by ion exchange reactions in the upper part of the soil profile.     

Fractionation of heavy metals and distribution of organic carbon in two contaminated soils amended with humic acids

The effects of humic acids (HAs) extracted from two different organic materials on the distribution of heavy metals and on organic-C mineralisation in two contaminated soils were studied in incubation experiments. Humic acids isolated from a mature compost (HAC) and a commercial Spaghnum peat (HAP) were added to an acid soil (pH 3.4; 966 mg kg(-1) Zn and 9,229 mg kg(-1) Pb as main contaminants) and to a calcareous soil (pH 7.7; 2,602 mg kg(-1) Zn and 1,572 mg kg(-1) Pb as main contaminants) at a rate of 1.1g organic-C added per 100g soil. The mineralisation of organic-C was determined by the CO(2) released during the experiment. After 2, 8 and 28 weeks of incubation the heavy metals of the soils were fractionated by a sequential extraction procedure. After 28 weeks of incubation, the mineralisation of the organic-C added was rather low in the soils studied (<8% of TOC in the acid soil; <10% of TOC in the calcareous soil). Both humic acids caused significant Zn and Pb immobilisation (increased proportion of the residual fraction, extractable only with aqua regia) in the acid soil, while Cu and Fe were slightly mobilised (increased concentrations extractable with 0.1M CaCl(2) and/or 0.5M NaOH). In the calcareous soil there were lesser effects, and at the end of the experiment only the fraction mainly related to carbonates (EDTA-extractable) was significantly increased for Zn and decreased for Fe in the humic acids treated samples. However, HA-metal interactions provoked the flocculation of these substances, as suggested by the association of the humic acids with the sand fraction of the soil. These results indicate that humic acid-rich materials can be useful amendments for soil remediation involving stabilisation, although a concomitant slight mobilisation of Zn, Pb and Cu can be provoked in acid soils.     

Heterogeneous response of central European streams to decreased acidic atmospheric deposition

We investigated the relations between mountain streamwater chemistry and atmospheric pollution in an arca of 1611 km2 of the Czech Republic by comparing concentrations of SO4. NO3, Cl, Ca and the pH at 432 localities at the time of high (1984-1986) and relatively low (1996-2000) acidic atmospheric deposition. Medians of Cl. SO4, and NO3 decreased by 17, 96 and 60 microeq l(-1), or by 23, 17 and 49%, respectively, during 12 +/- 2 years. The decreased Cl corresponds to decreased emission of industrial Cl (as HCl). The decreased stream SO4 was proportionally lower than the 71% decrease in S-emissions due to leaching of previously accumulated SO4 from soils and non-zero background concentrations. Decreases of NO3 up to 60% in streamwaters with pH < or = 6 was greater than the decrease of N emission in central Europe, about 35%. Extensive regional decrease of NO3 is surprising and is probably described for the first time. The difference in NO3 concentrations between the two periods was probably enhanced by (a) an increase of mineralisation of forest floor in the mid-1980s and (b) by higher uptake of N in the late-1990s. The median pH of the 432 streams did not change but the pH of the sub-population with pH < 6 in the mid-1980s recovered substantially. The pH of circum-neutral streams (pH > 6.5) decreased even as acidic atmospheric deposition decreased.     

Mechanisms of episodic acidification in low-order streams in Maine, USA

Five factors contribute to episodic depressions in pH and ANC during hydrologic events in low-order streams in Maine: (1) increases of up to 50 microeq litre(-1) NO3; (2) increases of up to 75 microeq litre(-1) organic acidity; (3) increases of as much as 0.3 in the anion fraction of SO4; (4) as much as 100 microeq litre(-1) acidity generated by the salt-effect in soils; and (5) typically < or = 40% dilution by increased discharge. In conjunction with increased discharge, factors 1, 2 or 4 appear necessary to depress pH to less than 5.0. The chemistry of individual precipitation events is irrelevant to the generation of acidic episodes, except those caused by high loading of neutral salts in coastal regions. Increases in discharge, but not necessarily in dilution of solutes, in combination with the chronically high SO4 from atmospheric deposition, provide the antecedent chemical conditions for episodic acidification. Differences in antecedent moisture conditions determine the processes that control output of either ANC or acidifying agents to aquatic systems.     

Kinetics and mechanism of TNT degradation in TiO2 photocatalysis

The photocatalytic degradation of TNT in a circular photocatalytic reactor, using a UV lamp as a light source and TiO(2) as a photocatalyst, was investigated. The effects of various parameters such as the initial TNT concentration, and the initial pH on the TNT degradation rate of TiO(2) photocatalysis were examined. In the presence of both UV light illumination and TiO(2) catalyst, TNT was more effectively degraded than with either UV or TiO(2) alone. The reaction rate was found to obey pseudo first-order kinetics represented by the Langmuir-Hinshelwood model. In the mineralization study, TNT (30 mg/l) photocatalytic degradation resulted in an approximately 80% TOC decrease after 150 min, and 10% of acetate and 57% of formate were produced as the organic intermediates, and were further degraded. NO(-)(3) NO(-)(2), and NH(+)(4) were detected as the nitrogen byproducts from photocatalysis and photolysis, and more than 50% of the total nitrogen was converted mainly to NO(-)(3)in the photocatalysis. However, NO(-)(3) did not adsorbed on the TiO(2) surface. TNT showed higher photocatalytic degradation efficiency at neutral and basic pH.     

Sulphur status in some Swedish podzols as influenced by acidic deposition and extractable organic carbon

To evaluate the changes in sulphur pools in response to acidic deposition, two studies were made-one in southwest Sweden where podzolic B horizons originally sampled in 1951 were resampled in 1989. At the Norrliden site, northern Sweden, sulphur pools in control plots were compared to plots that had been subjected to H(2)SO(4) application between 1971 and 1976. The results show that in southwest Sweden neither organic S nor extractable SO(4)(2-) increased significantly over the 38-year period, despite a decreasing pH and a high S deposition. At Norrliden, about 37% of the applied S was still remaining in the upper and central parts of the Bs horizon, most of which was inorganic sulphate. These contrasting results are explained by intrinsic differences in the soil organic carbon status between the sites-in southwest Sweden, organic carbon concentrations were high which inhibited SO(4)(2-) adsorption. Low organic carbon concentrations and high extractable Fe/Al concentrations promoted SO(4)(2-) adsorption and caused a low subsequent SO(4)(2-) desorption rate at the Norrliden site. The results suggest that sulphate adsorption may be an important mechanism which delays the response in soil chemistry to H(2)SO(4) deposition, provided that soil organic carbon concentrations are low. Organic S retention was not shown to be an important S retention mechanism in any of the sites studied.     

Decomposition and mineralization of cefaclor by ionizing radiation: kinetics and effects of the radical scavengers

There has been recent growing interest in the presence of antibiotics in different environmental sectors. One considerable concern is the potential development of antibiotic-resistant bacteria in the environment, even at low concentrations. Cefaclor, one of the beta-lactam antibiotics, is widely used as an antibiotic. Kinetic studies were conducted to evaluate the decomposition and mineralization of cefaclor using gamma radiation. Cefaclor, 30 mg/l, was completely degraded with 1,000 Gy of gamma radiation. At a concentration of 30 mg/l, the removal efficiency, represented by the G-value, decreased with increasing accumulated radiation dose. Batch kinetic experiments with initial aqueous concentrations of 8.9, 13.3, 20.0 and 30.0mg/l showed the decomposition of cefaclor using gamma radiation followed a pseudo first-order reaction, and the dose constant increased with lower initial concentrations. At a given radiation dose, the G-values increased with higher initial cefaclor concentrations. The experimental results using methanol and thiourea as radical scavengers indicated that ()OH radicals were more closely associated with the radiolytic decomposition of cefaclor than other radicals, such as e(aq)(-) or ()H. The radical scavenger effects were tested under O(2) and N(2)O saturations for the enhancement of the TOC percentage removal efficiencies in the radiolytic decomposition of cefaclor. Under O(2) saturation, 90% TOC removal was observed with 100,000 Gy. Oxygen is well known to play a considerable role in the degradation of organic substances with effective chain reaction pathways. According to the effective radical reactions, the enhanced TOC percentage removal efficiencies might be based on the fast conversion reactions of e(aq)(-) and ()H with O(2) into oxidizing radicals, such as O(2)(-) and HO(2)(), respectively. 100% TOC removal was obtained with N(2)O gas at 20,000 Gy, as reducing radicals, such as e(aq)(-) and ()H, are scavenged by N(2)O and converted into ()OH radicals, which have strong oxidative properties. The results of this study showed that gamma irradiation was very effective for the removal of cefaclor in aqueous solution. The use of O(2) or N(2)O, with radiation, shows promise as effective radical scavengers for enhancing the TOC or COD removal efficiencies in pharmaceutical wastewaters containing antibiotics. However, the biological toxicity and interactions between various chemicals during the radiolytic treatment, as well as treatments under conditions more representative of real wastewater will require further studies.     

Acid rain and nitrogen deposition in a sub-tropical watershed (Piracicaba): ecosystem consequences

High levels of wet N and acidic deposition were measured in southeast Brazil. In this study we addressed the sensitivity of water bodies and soils to acidification and N deposition in the Piracicaba River basin (12,400 km2). Average acid neutralization capacity (ANC) at 23 river sampling sites varied from 350 to 1800 microeq l(-1). Therefore, rivers and streams in the Piracicaba basin are well buffered, if the lower limit of 200 microeq l(-1) is assumed as an indication of poorly buffered waters. ANC is increased by untreated wastewaters discarded into rivers and streams of the region. Average NO3 concentrations varied from 20 to 70 microeq l(-1). At the most polluted river sites, NO3 concentration is not highest, however, probably due to NO3 reduction and denitrification. Most of the nitrogen in streams is also provided by wastewaters and not by wet deposition. The majority of the soils in the basin, however, are acidic with a low base cation content and high aluminum concentration. Therefore, soils in this basin are poorly buffered and, in areas of forest over sandy soils, acidification may be a problem.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

Internal acid buffering in San Joaquin Valley fog drops and its influence on aerosol processing

Although several chemical pathways exist for S(IV) oxidation in fogs and clouds, many are self-limiting: as sulfuric acid is produced and the drop pH declines, the rates of these pathways also decline. Some of the acid that is produced can be buffered by uptake of gaseous ammonia. Additional internal buffering can result from protonation of weak and strong bases present in solution. Acid titrations of high pH fog samples (median pH=6.49) collected in California's San Joaquin Valley reveal the presence of considerable internal acid buffering. In samples collected at a rural location, the observed internal buffering could be nearly accounted for based on concentrations of ammonia and bicarbonate present in solution. In samples collected in the cities of Fresno and Bakersfield, however, significant additional, unexplained buffering was present over a pH range extending from approximately four to seven. The additional buffering was found to be associated with dissolved compounds in the fogwater. It could not be accounted for by measured concentrations of low molecular weight (C₁–C₃) carboxylic acids, S(IV), phosphate, or nitrophenols. The amount of unexplained buffering in individual fog samples was found to correlate strongly with the sum of sample acetate and formate concentrations, suggesting that unmeasured organic species may be important contributors. Simulation of a Bakersfield fog episode with and without the additional, unexplained buffering revealed a significant impact on the fog chemistry. When the additional buffering was included, the simulated fog pH remained 0.3–0.7 pH units higher and the amount of sulfate present after the fog evaporated was increased by 50%. Including the additional buffering in the model simulation did not affect fogwater nitrate concentrations and was found to slightly decrease ammonium concentrations. The magnitude of the buffering effect on aqueous sulfate production is sensitive to the amount of ozone present to oxidize S(IV) in these high pH fogs.     

Degradation of azo dye Procion Red MX-5B by photocatalytic oxidation

The photocatalytic oxidation (PCO) of a monoazo dye Procion Red MX-5B under various physico-chemical conditions was investigated. Degradation of the dye by PCO was enhanced by augmentation in UV intensity, titanium dioxide and hydrogen peroxide concentrations but was inhibited by increase in initial dye concentration. The PCO process was affected by pH in a peculiar way. In the presence of 100 mg/l of TiO2 and the absence of H2O2, the highest reaction rate was observed when the initial pH was 10. With 500 mg/l of TiO2 and 10 mM of H2O2, the reaction was the fastest at initial pH of 3-5. The optimal conditions for the degradation of the dye, at an UV intensity of 17 mW/cm2, were determined to be: TiO2 concentration, 500 mg/l; initial H2O2 concentration, 10 mM; initial pH, 5.0. Monitoring of TOC loss showed that the dye was mineralized by 90% within 80 min under these conditions. Nevertheless, the persistence of a low level of TOC indicated that mineralization was not complete and dead-end product(s) which was (were) resistant to PCO might have accumulated.     

Mineralization of C.I. Reactive Yellow 84 in aqueous solution by sonolytic ozonation

The operational parameters and mechanism of mineralization of C.I. Reactive Yellow 84 (RY84), one of the azo dyes, in aqueous solution were investigated using sonolytic ozonation (US/O(3) oxidation). Of the pseudo-first-order degradation rate constants of TOC reduction, 9.0 x 10(-4), 7.3 x 10(-3) and 1.8 x 10(-2)min(-1) were observed with US, O3, and a combination of US and O3, respectively. These results illustrate that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone without considering the operating costs. With the initial pH value at 10.0, the ozone dose at 4.5 g h(-1), the energy density of ultrasound at 176 W l(-1), and the initial concentration of RY84 at 100 mg l(-1), the extent of mineralization measured as TOC loss was maximized. The variation of the concentrations of related ions (oxalate, formate, acetate, NO3(-), NO2(-), NH4(+), Cl(-), and SO4(2-)) during the reaction process was monitored. Other organic intermediates detected by GC/MS were N-methyleneaniline, phthalic acid, 4-hydroxyphthalic acid, isocyanatobenzene, aniline, 4-iminocyclohexa-2,5-dien-1-one, butene diacid and urea. Based on these findings, a tentative degradation pathway was proposed.     

Influence of sediment on the fate and toxicity of a polyethoxylated tallowamine surfactant system (MON 0818) in aquatic microcosms

The fate and toxicity of a polyethoxylated tallowamine (POEA) surfactant system, MON 0818, was evaluated in water-sediment microcosms during a 4-d laboratory study. A surfactant solution of 8 mg l(-1) nominal concentration was added to each of nine 72-l aquaria with or without a 3-cm layer of one of two natural sediments (total organic carbon (TOC) 1.5% or 3.0%). Control well water was added to each of nine additional 72-l aquaria with or without sediment. Water samples were collected from the microcosms after 2, 6, 24, 48, 72, and 96 h of aging to conduct 48-h toxicity tests with Daphnia magna and to determine surfactant concentrations. Elevated mortality of D. magna (43-83%) was observed in overlying water sampled from water-only microcosms throughout the 96-h aging period, whereas elevated mortality (23-97%) was only observed in overlying water sampled from water-sediment microcosms during the first 24h of aging. Measured concentrations of MON 0818 in water-only microcosms remained relatively constant (4-6 mg l(-1)) during the 96-h period, whereas the concentrations in overlying water from microcosms containing either of the two types of sediment dissipated rapidly, with half-lives of 13 h in the 3.0% TOC sediment and 18 h in the 1.5% TOC sediment. Both toxicity and the concentration of MON 0818 in overlying water decreased more rapidly in microcosms containing sediment with the higher percent TOC and clay and with a higher microbial biomass. Mortality of D. magna was significantly correlated with surfactant concentrations in the overlying water. These results indicate that the toxicity of the POEA surfactant in water rapidly declines in the presence of sediment due to a reduction in the surfactant concentration in the overlying water above the sediment.     

Fluoride removal performance of a novel Fe-Al-Ce trimetal oxide adsorbent

A trimetal oxide was developed as a fluoride adsorbent by coprecipitation of Fe(II), Al(III) and Ce(IV) salt solutions with a molar ratio of 1:4:1 under alkaline condition. The material retained amorphous structure and maintained relatively stable fluoride adsorption performance at calcination temperatures lower than 600 degrees C. The optimum pH range for fluoride adsorption was 6.0-6.5 and the adsorbent also showed high defluoridation ability around pH 5.5-7.0, which is preferable for actual application. A high fluoride adsorption capacity of 178 mg g(-1) was acquired under an equilibrium fluoride concentration of 84.5 mg l(-1), adsorbent dose of 150 mg l(-1) and pH 7.0. The adsorption isotherm could be better described by the two-site Langmuir model than the one-site model, suggesting the existence of two types of active sites on the adsorbent surface. Coexistence of high concentrations of phosphate or arsenate only led to partial inhibition of fluoride adsorption, which further suggests the existence of heterogeneous adsorption sites. Sulfate and chloride did not affect fluoride adsorption, and nitrate influenced it only when the concentration of NO(3)(-)-N exceeded 50 mg l(-1). A high desorption efficiency of 97% was achieved by treating fluoride loaded Fe-Al-Ce oxide with NaOH solution at pH 12.2. A column experiment using the adsorbent fabricated into 1mm pellets was performed at an initial fluoride concentration of 5.5 mg l(-1), space velocity of 5h(-1) and pH of 5.8, and 2240 bed volumes were treated with the effluent fluoride under 1.0 mg l(-1).     

混合硫酸盐还原菌代谢过程的影响因素

采用间歇实验,研究不同初始pH、Fe2+投加量、COD/SO24-及NO3-/SO24-比值等因素对SRB还原硫酸盐效果与速率的影响。实验结果表明:中性条件下(pH=7),硫酸盐的去除效果最佳,去除率达到84.66%,还原速率为15.07 mg/(L.h),在初始pH为4～9的范围内,体系具有较好的缓冲能力;当COD/SO24-比值为3时,反应209 h,硫酸盐去除率为85.33%,还原速率为8.16 mg/(L.h),随着反应的进行,体系的pH趋于中性;当溶液中有亚铁离子存在,且浓度为0～200 mg/L时可促进硫酸盐还原菌的生长,提高其对硫酸盐的去除率;NO3-对硫酸盐的还原有明显的抑制作用。