Characteristics and applications of controlled-release KMnO4 for groundwater remediation

In situ chemical oxidation (ISCO) using potassium permanganate (KMnO4) has been widely used as a practical approach for remediation of groundwater contaminated by chlorinated solvents like trichloroethylene. The most common applications are active flushing schemes, which target the destruction of some contaminant source by injecting concentrated permanganate (MnO4(-)) solution into the subsurface over a short period of time. Despite many promising results, KMnO4 flushing is often frustrated by inefficiency associated with pore plugging by MnO2 and bypassing. Opportunities exist for the development of new ISCO systems based on KMnO4. The new scheme described in this paper uses controlled-release KMnO4 (CRP) as an active component in the well-based reactive barrier system. This scheme operates to control spreading of a dissolved contaminant plume. Prototype CRP was manufactured by dispersing fine KMnO4 granules in liquid crystal polymer resin matrix. Scanning electron microscope data verified the formation of micro-scale (ID=20-200 microm) secondary capillary permeability through which MnO4(-) is released by a reaction-diffusion process. Column and numerical simulation data indicated that the CRP could deliver MnO4(-) in a controlled manner for several years without replenishment. A proof-of-concept flow-tank experiment and model simulations suggested that the CRP scheme could potentially be developed as a practical approach for in situ remediation of contaminated aquifers. This scheme may be suitable for remediation of sites where accessibility is limited or some low-concentration contaminant plume is extensive. Development of delivery systems that can facilitate lateral spreading and mixing of MnO4(-) with the contaminant plume is warranted.     

Model-based evaluation of controlled-release systems in the remediation of dissolved plumes in groundwater

Controlled-release, semi-passive reactive barrier systems have been recently developed as a long-term treatment option for controlling the spread of contaminant plumes in groundwater. This paper describes a new computer code, and applies it to study coupled processes of solute release, reaction, and mass transport in an in situ remediation scheme using the controlled release of potassium permanganate. Confidence with the modeling approach was developed by model verifications and simulating results of a pilot-scale test-cell experiment. Sensitivity analyses indicated the possibilities of treatment inefficiencies due to inability of transverse dispersion to mix the permanganate (MnO(4)(-)) within the zone of reaction, fluctuations in source strength due to variations in flow velocity, and the small length of treatment zone due to strong soil utilization of MnO(4)(-). Although problems associated with the fluctuating source strength and strong soil utilization can be addressed by optimizing the release rate, the inefficiency of transverse dispersion to create mixing could pose a serious limitation. Through a series of model simulations, a system of injection/withdrawal wells in a doublet arrangement was developed to facilitate lateral spreading and mixing of MnO(4)(-). A well-mixed, stable MnO(4)(-) zone with predetermined size (DxL=8m x 2m) and concentration ranges (1.5-20 mg l(-1)) was created by four 1-day injection/withdrawal pumping periods over 24 d. This type of mixing zone may persist for many years with periodic well mixing and replacements of exhausted controlled-release forms. Coupled use of the generalized code with field hydrologic data will help to optimize the design and operation of controlled-release systems in practice.     

Surfactant-enhanced oxidation of trichloroethylene by permanganate--proof of concept

Oxidative dechlorination of chlorinated solvents by permanganate is an emerging technology for remediation of groundwater contaminated with dissolved chlorinated contaminants. In this study, the enhancement of trichloroethylene (TCE) degradation by permanganate in aqueous solution in the presence of surfactant was evaluated through a continuous stir batch reactor system with the presence of permanganate as the limiting reagent and free phase TCE. The TCE degradation was determined by continuous monitoring the amount of chloride produced, which was then reverted to the rate of permanganate consumption. It was found that the chloride production, an indication of TCE degradation, followed a pseudo-first-order reaction kinetics with respect to KMnO(4) in the presence of free phase TCE. When no surfactants were present, the observed pseudo-first-order rate constant (k(obs)) was 0.08-0.19 min(-1) and the half-life (t(1/2)) was 4-9 min for MnO(4)(-). When the surfactant concentration was less than its critical micelle concentration (CMC), the k(obs) values increased to 0.42-0.46 min(-1) and the t(1/2) reduced to 1.5-1.7 min for MnO(4)(-). As the surfactant concentration was greater than the CMC, the k(obs) values increased to 0.56-0.58 min(-1) and the t(1/2) reduced to 1.2-1.3 min. The preliminary results showed that combination of permanganate with a proper type of surfactant can speed up contaminant removal.     

Quantification of potassium permanganate consumption and PCE oxidation in subsurface materials

A series of laboratory scale batch slurry experiments were conducted in order to establish a data set for oxidant demand by sandy and clayey subsurface materials as well as to identify the reaction kinetic rates of permanganate (MnO(4)(-)) consumption and PCE oxidation as a function of the MnO(4)(-) concentration. The laboratory experiments were carried out with 31 sandy and clayey subsurface sediments from 12 Danish sites. The results show that the consumption of MnO(4)(-) by reaction with the sediment, termed the natural oxidant demand (NOD), is the primary reaction with regards to quantification of MnO(4)(-) consumption. Dissolved PCE in concentrations up to 100 mg/l in the sediments investigated is not a significant factor in the total MnO(4)(-) consumption. Consumption of MnO(4)(-) increases with an increasing initial MnO(4)(-) concentration. The sediment type is also important as NOD is (generally) higher in clayey than in sandy sediments for a given MnO(4)(-) concentration. For the different sediment types the typical NOD values are 0.5-2 g MnO(4)(-)/kg dry weight (dw) for glacial meltwater sand, 1-8 g MnO(4)(-)/kg dw for sandy till and 5-20 g MnO(4)(-)/kg dw for clayey till. The long term consumption of MnO(4)(-) and oxidation of PCE can not be described with a single rate constant, as the total MnO(4)(-) reduction is comprised of several different reactions with individual rates. During the initial hours of reaction, first order kinetics can be applied, where the short term first order rate constants for consumption of MnO(4)(-) and oxidation of PCE are 0.05-0.5 h(-1) and 0.5-4.5 h(-1), respectively. The sediment does not act as an instantaneous sink for MnO(4)(-). The consumption of MnO(4)(-) by reaction with the reactive species in the sediment is the result of several parallel reactions, during which the reaction between the contaminant and MnO(4)(-) also takes place. Hence, application of low MnO(4)(-) concentrations can cause partly oxidation of PCE, as the oxidant demand of the sediment does not need to be met fully before PCE is oxidised.     

Impact of injection system design on ISCO performance with permanganate--mathematical modeling results

In situ chemical oxidation (ISCO) using permanganate (MnO(4)(-)) can be a very effective technique for remediation of soil and groundwater contaminated with chlorinated solvents. However, many ISCO projects are less effective than desired because of poor delivery of the chemical reagents to the treatment zone. In this work, the numerical model RT3D was modified and applied to evaluate the effect of aquifer characteristics and injection system design on contact and treatment efficiency. MnO(4)(-) consumption was simulated assuming the natural oxidant demand (NOD) is composed of a fraction that reacts instantaneously and a fraction that slowly reacts following a 2nd order relationship where NOD consumption rate increases with increasing MnO(4)(-) concentration. MnO(4)(-) consumption by the contaminant was simulated as an instantaneous reaction. Simulation results indicate that the mass of permanganate and volume of water injected has the greatest impact on aquifer contact efficiency and contaminant treatment efficiency. Several small injection events are not expected to increase contact efficiency compared to a single large injection event, and can increase the amount of un-reacted MnO(4)(-) released down-gradient. High groundwater flow velocities can increase the fraction of aquifer contacted. Initial contaminant concentration and contaminant retardation factor have only a minor impact on volume contact efficiency. Aquifer heterogeneity can have both positive and negative impacts on remediation system performance, depending on the injection system design.     

Catchment acidification-from the top down

Three main factors define the speed of catchment acidification: the total input of pollutants; the thickness and character of soils, including the nature of the bedrock; and the size of subcatchments. The aerial input of pollutants in the Harz is among the highest in Central Europe (e.g. SO4-S: 22-70 kg (ha year)(-1); NO3-N: 9-10 kg (ha year)(-1); NH4-N: 10-15 kg (ha year)(-1) and Cd: 2.6-8.7 g (ha year)(-1); Cu: 34-125 g (ha year)(-1); Pb: 150-380 g (ha year)(-1); Zn: 105-560 g (ha year)(-1)). Thick soil profiles (2-4 m) acidify from the top down. Whether the soils will neutralize incoming acids depends on their buffering capacity. The small headwater subcatchments acidify first and subsequently release acidic water with pH values down to < or = 40. Four brook zones can be divided by the composition of their biocoenoses. The latter depend on the degree of acidification. These zones are also characterized by different hydrochemical conditions.     

Characterization and optimization of long-term controlled release system for groundwater remediation: a generalized modeling approach

A well-based reactive barrier system using controlled-release KMnO4 has been recently developed as a long-term in situ treatment option for plumes of dense and non-aqueous phase liquids in groundwater. In order to take advantage of the merits of controlled release systems (CRS) in environmental remediation, the release behavior needs to be optimized for the hydrologic and environmental conditions of target treatment zone. Where release systems are expected to be operated over long times, like for the reactive barriers, it may only be practical to describe the long-term behavior numerically. We developed a numerical model capable of describing release characteristics associated with variable forms and structures of long-term CRS. Sensitivity analyses and illustrative simulations showed that the release kinetics and durations would be constrained by changes in agent solubility, bulk diffusion coefficients, or structures of the release devices. The generality of the numerical model was demonstrated through simulations for CRS with monolithic and double-layered matrices. The generalized model was then used for actual design and analyses of an encapsulated-matrix CRS, which can yield constant release kinetics for several years. A well-based reactive barrier system (4.05 x 10(3)m3) using the encapsulated-matrix CRS can release approximately 1.65 kg of active agent (here MnO4(-)) daily over the next 6.6 yr, creating prolonged reaction zone in the subsurface. The generalized model-based, target-specific approach using the long-term CRS could provide practical tool for improving the efficacy of advanced in situ remediation schemes such as in situ chemical oxidation, bioremediation, or in situ redox manipulation. Development of techniques for adjusting the bulk diffusion coefficients of the release matrices and facilitating the lateral spreading of the released agent is warranted.     

Manganese and trace-metal mobility under reducing conditions following in situ oxidation of TCE by KMnO4: a laboratory column experiment

The stability of Mn oxides, and the potential for mobilization of associated trace metals, were assessed by simulating the onset of microbially-mediated reducing conditions in a continuous-flow column experiment. The column had previously been used for an in situ chemical oxidation (ISCO) experiment in which trichloroethylene was reacted with permanganate in the presence of aqueous trace metals, which produced Mn oxyhydroxides (MnO(x)) that sequestered the trace metals and coated the column sand. The column influent solution represented the incursion of ambient groundwater containing dissolved organic carbon (DOC) into an ISCO treatment zone. The influx of DOC-containing groundwater initiated a series of cation-exchange, surface-complexation and reductive-dissolution reactions that controlled the release of aqueous metals from the system. Peak concentrations in the effluent occurred in the order Na, Mo, Cr, Zn, K, Mn, Fe, Pb, Mg, Ni, Cu and Ca. Manganese release from the column was controlled by a combination of cation exchange, reductive dissolution and precipitation of rhodochrosite. The trend in Fe concentrations was similar to that of Mn, and also resulted from a combination of reductive dissolution and cation exchange. Cation exchange and/or surface-complexation were the primary mechanisms controlling Cu, Ni, Mo and Pb release to solution, while Zn and Cr concentrations did not display coherent trends. Although metal release from the treatment zone was evident in the data, concentrations of trace metals remained below 0.05 mg L(-1) with the exception of Mo which reached concentrations on the order of 1 mg L(-1). The establishment of anaerobic conditions in ISCO-treated aquifers may result in a prolonged flux of aqueous Mn(II), but with the exception of MoO(4)(2-), it is unlikely that trace metals sequestered with MnO(x) during ISCO will be released to the groundwater in elevated concentrations.     

In-situ oxidation of trichloroethene by permanganate: effects on porous medium hydraulic properties

In-situ oxidation of dense nonaqueous-phase liquids (DNAPLs) by strong oxidants such as potassium permanganate (KMnO4) has been proposed as a possible DNAPL remediation strategy. In this study, we investigated the effects of in-situ trichloroethene (TCE) oxidation by KMnO4 on porous medium hydraulic properties. In particular, we wanted to determine the overall effects of concurrent solid phase (MnO2) precipitation, gas (CO2) evolution and TCE dissolution resulting from the oxidation reaction on the porous medium's aqueous-phase relative permeability, krw. Three TCE removal experiments were conducted in a 95-cm long, 5.1-cm i.d. glass column, which was homogeneously packed with well-characterized 30/40-mesh silica sand. TCE was emplaced in the sand-pack in residual, entrapped form through a sequence of water/TCE imbibition and drainage steps. The column was then flushed under constant aqueous flux conditions for up to 104 h with either deionized water (reference experiment), deionized water containing 5 mM KMnO4 or deionized water containing 5 mM KMnO4 and 300 mM Na2HPO4. Aqueous-phase relative permeabilities were computed from measured flow rates and measurements of aqueous-phase pressure head, h obtained using pressure transducers connected to tensiometers distributed along the column length. A dual-energy gamma radiation system was used to monitor changes in fluid saturation that occurred during each experiment. In addition, column effluent samples were collected for chemical analyses. Dissolution of TCE during deionized water flushing led to an increase in krw by approximately 22% and a local reduction in h. On the other hand, vigorous CO2 gas production and precipitation of MnO2 was visually observed during flushing with deionized water that contained 5 mM KMnO4. As a consequence, krw declined by approximately 96% and h increased locally by more than 1000 cm H2O during the first 24 h of the experiment, causing sand-pack ruptures and pump failure. Conversely, less CO2 gas production and MnO2 precipitation was visually observed during flushing with deionized water that contained 5 mM KMnO4 and 300 mM Na2HPO4. Consequently, only small increases in h (< 15 cm H2O) were observed in this experiment due to a reduction in krw of approximately 53%. While we must attribute changes in h due to variations in krw to our specific experimental design (constant aqueous flux, one-dimensional flow experiments), these experiments nevertheless confirm that successful application of in situ chemical oxidation of TCE requires consideration of detrimental processes such as MnO2 precipitation and CO2 gas formation. In addition, our results indicate that utilization of a buffered oxidant solution may improve the effectiveness of in-situ oxidation of TCE by KMnO4 in otherwise weakly buffered porous media.     

Simulation modeling for nitrogen removal and experimental estimation of mass fractions of microbial groups in single-sludge system

Nitrification-denitrification in a single-sludge nitrogen removal system (SSNRS; with a sufficient carbon source for denitrification) was performed. With an increase in the mixed liquor recycle ratio (R(m)) from 1 to 2, the total nitrogen (TN) removal efficiency at a lower volumetric loading rate (VLR=0.21 NH(4)(+)-N m(-3) d(-1)) increased, but the TN removal efficiency at a higher VLR (0.35 kg NH(4)(+)-N m(-3) d(-1)) decreased. A kinetic model that accounts for the mass fractions of Nitrosomonas, Nitrobacter, nitrate reducer and nitrite reducer (f(n1), f(n2), f(dn1), and f(dn2)) in the SSNRS and an experimental approach for the estimation of the mass fractions of nitrogen-related microbial groups are also proposed. The estimated f(dn1) plus f(dn2) (0.65-0.83) was significantly larger than the f(n1) plus f(n2) (0.28-0.32); the f(n1) (0.21-0.26) was larger than the f(n2) (0.05-0.07); and the f(dn1) (0.32-0.45) varied slightly with the f(dn2) (0.33-0.38). At the lower VLR, the f(dn1) plus f(dn2) increased with increasing R(m); however at the higher VLR, the f(dn1) plus f(dn2) did not increase with increasing R(m). By using the kinetic model, the calculated residual NH(4)(+)-N and NO(2)(-)-N in the anoxic reactor and NO(2)(-)-N and NO(3)(-)-N in the aerobic reactor were in fairly good agreement with the experimental data; the calculated NO(3)(-)-N in the anoxic reactor was over-estimated and the calculated NH(4)(+)-N in the aerobic reactor was under-estimated.     

Kinetics and mechanism of nitrite oxidation by hypochlorous acid in the aqueous phase

The rate coefficient for the reaction of nitrite with hypochlorite and hypochlorous acid has been studied using spectrophotometric measurements. The reaction rate has been determined in a wide range of H(+) concentration (5< or =-log[H(+)]< or =11). The kinetics were carried out as a function of NO(2)(-), H(+) and total hypochlorite ([HOCl](total)=[HOCl]+[ClO(-)]+[ClNO(2)]) concentrations. The observed overall rate law is described by: -d[HClO](T)dt=[a[NO(2)(-)](2)+b[NO(2)(-)]][H(+)](2)c+d[H(+)]+e[NO(2)(-)][H(+)](2)[HOCl](total)At T=298 K and in Na(2)SO(4) at an ionic strength (I=1.00 M), we obtained using a nonlinear fitting procedure: a=(1.83+/-0.36)x10(7) s(-1), b=(1.14+/-0.23)x10(5) Ms(-1), c=(1.12+/-0.17)x10(-13) M, d=(1.43+/-0.29)x10(-6) M(2) and e=(1.41+/-0.28)x10(3) M where the errors represent 2sigma. According to the overall rate law, a/b=k(1)/k(3), b/e=k(3), c=K(w), d/c=K(a), d=K(a)K(w) and e=K(1)K(a). In Na(2)SO(4) at an ionic strength (I=1.00 M), the values of K(1) and K(a) are (1.1+/-0.1)x10(-4) and 1.28x10(7) M(-1), respectively. A mechanism is proposed for the NO(2)(-) oxidation which involves the reversible initial step: NO(2)(-)+HOCl left harpoon over right harpoon ClNO(2)+OH(-) (K(1)), while ClNO(2) undergoes the two parallel reactions: attack by NO(2)(-) (k(1)) and hydrolysis (k(3)). ClNO(2) and N(2)O(4) are proposed as important intermediates as they control the mechanism. The rate coefficients k(1) and k(3) have been determined at different ionic strengths in NaCl and Na(2)SO(4). The influence of the ionic strength and ionic environment has been studied in this work.     

Cosolvent-enhanced chemical oxidation of perchloroethylene by potassium permanganate

A laboratory study was conducted to examine cosolvent-enhanced in-situ chemical oxidation (ISCO) of perchloroethylene (PCE) using potassium permanganate (KMnO4). The conceptual basis for this new technique is to enhance permanganate oxidation of dense non-aqueous phase liquids (DNAPLs) with the addition of a cosolvent, thereby increasing DNAPL solubility while avoiding mobilization. Among 17 cosolvent candidates screened, tertiary butyl alcohol (TBA) and acetone were the most stable in the presence of KMnO4, both of which increased PCE aqueous solubility significantly, and therefore are suitable to be used as cosolvent in this study. Batch experiments indicated that the second-order rate constant for PCE oxidation by potassium permanganate was 0.043+/-0.002 M(-1) s(-1) in the purely aqueous (no cosolvent) solution. In the presence of 20% cosolvent (volume fraction=fc=0.2), the rate constant decreased to 0.036+/-0.003 M(-1) s(-1) with TBA and to 0.031+/-0.002 M(-1) s(-1) with acetone. However, in the presence of free-phase PCE, chloride ion concentration from PCE oxidation in acetone/water solutions (fc=0.2) was about twice that in aqueous solutions, indicating that the increase in PCE solubility more than compensated for the decrease in reaction rate constant, such that the oxidation efficiency of PCE was increased with cosolvent. A complete chlorine mass balance was observed in the aqueous system, whereas approximately 70% was obtained in TBA/water or acetone/water (fc=0.2). In soil columns containing residual DNAPL and subjected to isocratic flushing with step-wise increases in f(c) cosolvent, TBA at fc=0.2 resulted in PCE mobilization, whereas acetone at fc相似文献   

Effect of recycle-to-influent ratio on activities of nitrifiers and denitrifiers in a combined UASB-activated sludge reactor system

A laboratory study using a combined upflow anaerobic sludge bed (UASB)-activated sludge (AS) reactor system was undertaken to explore the effect of recycle-to-influent ratio (R(e)=1, 2, and 3) on the activities of nitrifiers and denitrifiers. Suspended-solids pre-settled piggery wastewater was used as the substrate-feed wastewater. At the R(e) of 1-3, the combined reactor system achieved efficient removal of COD (96-97%), TKN (100%) and total nitrogen TN (54-77%). Methanogenesis occurred with nearly-complete denitrification in the UASB reactor, whereas complete nitrification took place in the AS reactor. A higher R(e) (i.e., accompanied with a shorter solids retention time) resulted in a larger amount of high-activity denitrifiers and thereby achieved a higher TN removal efficiency. Compact granules and a high biomass concentration in the UASB reactor were observed. At the R(e) of 1-3, the maximum specific reaction rate of nitrifiers (0.45-0.49 NH(4)(+)-NmgVSS(-1)d(-1)) and the specific nitrification rates of mixed culture (0.18-0.22mg NH(4)(+)-NmgVSS(-1)d(-1)) in the AS reactor varied slightly; whereas the maximum specific reaction rate of denitrifiers (0.18-0.27mg NO(x)(-)-NmgVSS(-1)d(-1)) and the specific denitrification and COD removal rates of mixed culture (0.025-0.050mg NO(x)(-)-NmgVSS(-1)d(-1); 0.24-0.31mgCODmgVSS(-1)d(-1)) in the UASB reactor increased with increasing R(e). The primary finding of the study is that the combined UASB-AS reactor system should be operated at a higher R(e) to maintain high-activity denitrifiers to remove organic materials and nitrogen from piggery wastewater.     

Coupling permanganate oxidation with microbial dechlorination of tetrachloroethene.

For sites contaminated with chloroethene non-aqueous-phase liquids, designing a remediation system that couples in situ chemical oxidation (ISCO) with potassium permanganate (KMnO4) and microbial dechlorination may be complicated because of the potentially adverse effects of ISCO on anaerobic bioremediation processes. Therefore, one-dimensional column studies were conducted to understand the effect of permanganate oxidation on tetrachloroethene (PCE) dechlorination by the anaerobic mixed culture KB-1. Following the confirmation of PCE dechlorination, KMnO4 was applied to all columns at a range of concentrations and application velocities to simulate varied distances from oxidant injection. Immediately following oxidation, reductive dechlorination was inhibited; however, after passing several pore volumes of sterile growth medium through the columns after oxidation, a rebound of PCE dechlorination activity was observed in every inoculated column without the need to reinoculate. The volume of medium required for a rebound of dechlorination activity differed from 1.1 to 8.1 pore volumes (at a groundwater velocity of 4 cm/d), depending on the specific condition of oxidant application.     

Concentrations of ammonia and nitrogen dioxide at roadside verges, and their contribution to nitrogen deposition

Bimonthly integrated measurements of NO2 and NH3 have been made over one year at distances up to 10 m away from the edges of roads across Scotland, using a stratified sampling scheme in terms of road traffic density and background N deposition. The rate of decrease in gas concentrations away from the edge of the roads was rapid, with concentrations falling by 90% within the first 10 m for NH3 and the first 15 m for NO2. The longer transport distance for NO2 reflects the production of secondary NO2 from reaction of emitted NO and O3. Concentrations above the background, estimated at the edge of the traffic lane, were linearly proportional to traffic density for NH3 (microg NH3 m(-3) = 1 x 10(-4) x numbers of cars per day), reflecting emissions from three-way catalysts. For NO2, where emissions depend strongly on vehicle type and fuel, traffic density was calculated in terms of 'car equivalents'; NO2 concentrations at the edge of the traffic lane were proportional to the number of car equivalents (microg NO2 m(-3) = 1 x 10(-4) x numbers of car equivalents per day). Although absolute concentrations (microg m(-3)) of NH3 were five times smaller than for NO2, the greater deposition velocity for NH3 to vegetation means that approximately equivalent amounts of dry N deposition to road side vegetation from vehicle emissions comes from NH3 and NO2. Depending on traffic density, the additional N deposition attributable to vehicle exhaust gases is between 1 and 15 kg N ha(-1) y(-1) at the edge of the vehicle lane, falling to 0.2-10 kg N ha(-1) y(-1) at 10 m from the edge of the road.     

Trout farm effluents: characterization and impact on the receiving streams

Effluents from three rainbow trout (Oncorhynchus mykiss) farms located in Northern Portugal were characterized and their impact on the receiving streams was evaluated. Mean fish productions in the studied fish farms were 15, 55 and 500 t of trout per year, respectively. The feeding water was abstracted from Fornelo, Inha and Coura Rivers, at flow rates ranging from 1.2 (15 t year(-1) fish farm) to 4.8 litre s(-1) per ton annual fish production (500 t year(-1) fish farm). As the water flows through the farms, net variations in the chemical characteristics were observed: a mean reduction in the dissolved oxygen (DO) concentration between 0.7 and 2.4 mg litre(-1); mean increases between 1.9 and 3.2 mg CaCO3 litre(-1) for total alkalinity, between 0.9 and 14 mg litre(-1) for BOD5, between 0.27 and 1.46 mg litre(-1) for ammonia nitrogen (NH4-N), between 0.060 and 0.579 mg litre(-1) for soluble phosphorus (PO4-P) and less than 16 mg litre(-1) for suspended solids; variations in the pH value and nitrate nitrogen concentration were not statistically significant (p<0.05). At the 500 t year(-1) fish farm it was also possible to detect net increases of total hardness (3.2 mg CaCO3 litre(-1)), electric conductivity (19 mS cm(-1)) and permanganate value (3.6 mgO2 litre(-1)). At the other farms net variations in these parameters were not significant. Net mass flow variations reported to the annual fish production are presented. The DO mass flow decreased, on average, between 255 and 549 g t(-1) of fish per day. The mean daily BOD5 increase ranged from 353 to 1510 g t(-1) of fish. The corresponding ranges for the other parameters were 105-157 g t(-1) for NH4-N, 24-62 g t(-1) for PO4-P, 348-1035 g CaCO3 t(-1) for total alkalinity and 224 x 10(6)-506 x 10(6) t(-1) for mesophilic bacteria. Daily net variations of suspended solids, total hardness, electric conductivity and permanganate value were below 1753 g t(-1), 342 g CaCO3 t(-1), 2081 mS cm t(-1) and 392 gO2 t(-1), respectively. Longitudinal concentration profiles for the most relevant parameters show the impact of the effluent discharges on the physico-chemical and bacteriological river water quality downstream from the trout farms. Analyzing the situations from a purely chemical point of view, the polluted stretches were 3, 5 and 12 km long downstream from the effluent discharges, respectively. The microbiological contamination extended over longer distances.     

Kinetic assessment of the potassium ferrate(VI) oxidation of antibacterial drug sulfamethoxazole

Sulfamethoxazole (SMX), a worldwide-applied antibacterial drug, was recently found in surface waters and in secondary wastewater effluents, which may result in ecotoxical effects in the environment. Herein, removal of SMX by environmentally-friendly oxidant, potassium ferrate(VI) (K(2)FeO(4)), is sought by studying the kinetics of the reaction between Fe(VI) and SMX as a function of pH (6.93-9.50) and temperature (15-45 degrees C). The rate law for the oxidation of SMX by Fe(VI) is first-order with respect to each reactant. The observed second-order rate constant decreased non-linearly from 1.33+/-0.08 x 10(3) M(-1)s(-1) to 1.33+/-0.10 x 10(0) M(-1)s(-1) with an increase of pH from 7.00 to 9.50. This is related to protonation of Fe(VI) (HFeO(4)(-) <==> H(+) + FeO(4)(2-); pK(a,HFeO(4)) = 7.23) and sulfamethoxazole (SH <==> H(+) + S(-); pK(a,SH)=5.7). The estimated rate constants were k(11)(HFeO(4)(-) + SH) = 3.0 x 10(4) M(-1)s(-1), k(12)(HFeO(4)(-) + S(-)) = 1.7 x 10(2) M(-1)s(-1), and k(13) (FeO(4)(2-) + SH) = 1.2 x 10(0) M(-1)s(-1). The energy of activation at pH 7.0 was found to be 1.86+/-0.04 kJ mol(-1). If excess potassium ferrate(VI) concentration (10 microM) is used than the SMX in water, the half-life of the reaction using a rate constant obtained in our study would be approximately 2 min at pH 7. The reaction rates are pH dependent; thus, so are the half-lives of the reactions. The results suggest that K(2)FeO(4) has the potential to serve as an oxidative treatment chemical for removing SMX in water.     

Intermediate-scale 2D experimental investigation of in situ chemical oxidation using potassium permanganate for remediation of complex DNAPL source zones

In situ chemical oxidation is a technology that has been applied to speed up remediation of a contaminant source zone by inducing increased mass transfer from DNAPL sources into the aqueous phase for subsequent destruction. The DNAPL source zone can consist of one or more individual sources that may be present as an interconnected pool of high saturation, as a region of disconnected ganglia at residual saturation, or as combinations of these two morphologies. Potassium permanganate (KMnO(4)) is a commonly employed oxidant that has been shown to rapidly destroy DNAPL compounds like PCE and TCE following second-order kinetics in an aqueous system. During the oxidation of a target DNAPL compound, or naturally occurring reduced species in the subsurface, manganese oxide (MnO(2)) solids are produced. Research has shown that these manganese oxide solids may result in permeability reductions in the porous media thus reducing the ability for oxidant to be transported to individual DNAPL sources. It can also occur at the DNAPL-water interface, decreasing contact of the oxidant with the DNAPL. Additionally, MnO(2) formation at the DNAPL-water interface, and/or flow-bypassing as a result of permeability reductions around the source, may alter the mass transfer from the DNAPL into the aqueous phase, potentially diminishing the magnitude of any DNAPL mass depletion rate increase induced by oxidation. An experiment was performed in a two-dimensional (2D) sand-filled tank that included several discrete DNAPL source zones. Spatial and temporal monitoring of aqueous PCE, chloride, and permanganate concentrations was used to relate changes in mass depletion of, and mass flux, from DNAPL residual and pool source zones to chemical oxidation performance and MnO(2) formation. During the experiment, permeability changes were monitored throughout the 2D tank and these were related to MnO(2) deposition as measured through post-oxidation soil coring. Under the conditions of this experiment, MnO(2) formation was found to reduce permeability in and around DNAPL source zones resulting in changes to the overall flow pattern, with the effects depending on source zone configuration. A pool with little or no residual around it, in a relatively homogeneous flow field, appeared to benefit from resulting MnO(2) pore-blocking that substantially reduced mass transfer from the pool even though there was relatively little PCE mass removed from the pool. In contrast, a pool with residual around it (in a more typical heterogeneous flow field) appeared to undergo increased mass transfer as MnO(2) reduced permeability, altering the water flow and increasing the mixing at the DNAPL-water interface. Further, the magnitude of increased PCE mass depletion during oxidation appeared to depend on the PCE source configuration (pool versus ganglia) and decreased as MnO(2) was formed and deposited at the DNAPL-water interface. Overall, the oxidation of PCE mass appeared to be rate-limited by the mass transfer from the DNAPL to aqueous phase.     

Fluxes of oxidised and reduced nitrogen above a mixed coniferous forest exposed to various nitrogen emission sources

Concentrations of nitrogen gases (NH(3), NO(2), NO, HONO and HNO(3)) and particles (pNH(4) and pNO(3)) were measured over a mixed coniferous forest impacted by high nitrogen loads. Nitrogen dioxide (NO(2)) represented the main nitrogen form, followed by nitric oxide (NO) and ammonia (NH(3)). A combination of gradient method (NH(3) and NO(x)) and resistance modelling techniques (HNO(3), HONO, pNH(4) and pNO(3)) was used to calculate dry deposition of nitrogen compounds. Net flux of NH(3) amounted to -64 ng N m(-2) s(-1) over the measuring period. Net fluxes of NO(x) were upward (8.5 ng N m(-2) s(-1)) with highest emission in the morning. Fluxes of other gases or aerosols substantially contributed to dry deposition. Total nitrogen deposition was estimated at -48 kg N ha(-1) yr(-1) and consisted for almost 80% of NH(x). Comparison of throughfall nitrogen with total deposition suggested substantial uptake of reduced N (+/-15 kg N ha(-1) yr(-1)) within the canopy.     

Kinetics and mechanism of oxidation of tetrachloroethylene with permanganate

The kinetics, reaction pathways and product distribution of oxidation of tetrachloroethylene (PCE) by potassium permanganate (KMnO4) were studied in phosphate-buffered solutions under constant pH, isothermal, completely mixed and zero headspace conditions. Experimental results indicate that the reaction is first-order with respect to both PCE and KMnO4 and has an activation energy of 9.3+/-0.9 kcal/mol. The second-order rate constant at 20 degrees C is 0.035+/-0.004 M(-1) s(-1), and is independent of pH and ionic strength (I) over a range of pH 3-10 and I approximately 0-0.2 M, respectively. The PCE-KMnO4 reaction may proceed through further oxidation and/or hydrolysis reaction pathways, greatly influenced by the acidity of the solution, to yield CO2(g), oxalic acid, formic acid and glycolic acid. Under acidic conditions (e.g., pH 3), the further oxidation pathway will dominate and PCE tends to be directly mineralized into CO2 and chloride. Under neutral (e.g., pH 7) and alkaline conditions (e.g., pH 10), the hydroxylation pathway dominates the reaction and PCE is primarily transformed into oxalic acid prior to complete PCE mineralization. Moreover, all chlorine atoms in PCE are rapidly liberated during the reaction and the rate of chloride production is very close to the rate of PCE degradation.