Sorption of Pb2+ from aqueous solution using polyethylene and polyvinylchloride wastes as adsorbents: a comparative study

This study gives insight into the sorption potential of Pb²⁺ from aqueous solution using polyethylene and polyvinylchloride wastes as adsorbent. The polymer samples were characterised by X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM) for their morphological features. Kinetic, equilibrium and thermodynamic batch adsorption experiments investigated varying parameters such as: concentration, temperature and time. The SEM images of the polymers revealed irregular small size particles, indicating a high surface area and porosities facilitating sorption. The adsorption studies documented relatively rapid Pb²⁺ uptake by the polymers that are mainly diffusion controlled, with a second order kinetic process. The sorption of Pb²⁺ onto the polymer surfaces was thermodynamically favoured at relatively low temperature (low energy). Thermodynamic studies demonstrated exothermic physi-sorption mechanisms for Polyethylene (PE) and Polyvinylchloride (PVC).     

Use of stable nitrogen isotope fractionation to estimate denitrification in small constructed wetlands treating agricultural runoff

Constructed wetlands (CWs) in the agricultural landscape reduce non-point source pollution through removal of nutrients and particles. The objective of this study was to evaluate if measurements of natural abundance of (15)NO(3)(-) can be used to determine the fate of NO(3)(-) in different types of small CWs treating agricultural runoff. Nitrogen removal was studied in wetland trenches filled with different filter materials (T1--sand and gravel; T3--mixture of peat, shell sand and light-weight aggregates; T8--barley straw) and a trench formed as a shallow pond (T4). The removal was highest during summer and lowest during autumn and winter. Trench T8 had the highest N removal during summer. Measurements of the natural abundance of (15)N in NO(3)(-) showed that denitrification was not significant during autumn/winter, while it was present in all trenches during summer, but only important for nitrogen removal in trench T8. The (15)N enrichment factors of NO(3)(-) in this study ranged from -2.5 to -5.9 per thousand (T3 and T8, summer), thus smaller than enrichment factors found in laboratory tests of isotope discrimination in denitrification, but similar to factors found for denitrification in groundwater and a large CW. The low enrichment factors compared to laboratory studies was attributed to assimilation in plants/microbes as well as diffusion effect. Based on a modified version of the method presented by Lund et al. [Lund LJ, Horne AJ, Williams AE, Estimating denitrification in a large constructed wetland using stable nitrogen isotope ratios. Ecol Engineer 2000; 14: 67-76], denitrification and assimilation were estimated to account for 53 to 99 and 1 to 47%, respectively, of the total N removal during summer. This method is, however, based on a number of assumptions, and there is thus a need for a better knowledge of the effect of plant uptake, microbial assimilation as well as nitrification on N isotopic fractionation before this method can be used to evaluate the contribution of dinitrification in CWs.     

The use of Bassia indica for salt phytoremediation in constructed wetlands

The treatment and reuse of wastewater in constructed wetlands offers a low-cost, environmentally-friendly alternative for common engineered systems. Salinity in treated wastewater is often increased, especially in arid and semi-arid areas, and may harm crops irrigated from wetlands. We have strong evidence that halophyte plants are able to reduce the salinity of wastewater by accumulating salts in their tissues. Bassia indica is an annual halophyte with unique adaptations for salt tolerance. We performed three experiments to evaluate the capability of B. indica for salt phytoremediation as follows: a hydroponic system with mixed salt solutions, a recirculated vertical flow constructed wetland (RVFCW) with domestic wastewater, and a vertical flow constructed wetland (VFCW) for treating goat farm effluents. B. Indica plants developed successfully in all three systems and reduced the effluent salinity by 20-60% in comparison with unplanted systems or systems planted with other wetland plants. Salinity reduction was attributed to the accumulation of salts, mainly Na and K, in the leaves. Our experiments were carried out on an operative scale, suggesting a novel treatment for green desalination in constructed wetlands by salt phytoremediation in desert regions and other ecosystems.     

Sorption of organics by Selenastrum capricornutum

The sorption of eight organic compounds by a representative green alga, Selenastrum capricornutum, was determined by gas-liquid chromatography using a series of linear model experiments. The log₁₀ bioconcentration factors (BCF), defined as the ratio of the concentration on in the algae to the concentration in the aqueous medium, are as follows: benzene, 3.32; toluene, 3.18; chlorobenzene, 3.69; 1,2-dichlorobenzene, 4.17; naphthalene, 4.10; phenanthrene, 4.38; di-n-butylphthalate, 4.36 and pyrene, 4.56. The relation of log₁₀ BCF correlation with log₁₀ octanol-water partition coefficient was determined as log₁₀ BCF = 0.46 log₁₀ P + 2.36.     

Phosphorus retention capacity of filter media for estimating the longevity of constructed wetland

The filter medium could be selected and the longevity of the filter medium by the phosphorus saturation could be predicted in the constructed wetland system, accordingly proposing the scheme to remove the phosphorus for a long period. The phosphorus adsorption capacities of various filter media were investigated in relation to the size and types of filter media to screen the optimal condition. The objective of this study was to evaluate the constructed wetland longevity by improving P adsorption capacity. The maximum P adsorption capacities of filter media A (4-10 mm), B (2-4 mm), and C (0.1-2 mm) were 7.7, 11.6, and 22.5 mg/kg, respectively, showing that they increased as the filter media size decreased. Among the experimental media, the optimal filter media size was 0.1-2 mm. When Ca, Mg, Al and Fe were added to the filter medium C, which is the optimal filter medium, the addition of Ca improved mostly the P adsorption capacity. In the alternative proposal to use these facts, the oyster shell was added to the filter medium and the P adsorption capacity was examined: adding 2% oyster shell increased the P adsorption capacity from 23 to 36 mg/kg. In the column where the oyster shell was mixed, when the oyster shell content was 5%, 10%, 20%, 40%, 60%, 80%, and 100% in the filter medium C, the respective saturation times of the P adsorption were about 6, 9, 17, 30, 43, 56, and 70 days. When the oyster shell content was 0%, 5%, 10%, 20%, 40%, 60%, 80%, and 100% after 1 month in the column, the P adsorption amount was about 180, 600, 1560, 4280, 6157, 7089, 7519, and 7925 mg/kg, respectively. The increment of the P adsorption amount was small if the oyster shell content was 60% or more, because the filter medium with more than 60% oyster shell content did not approach the saturation time by the P adsorption yet. The P adsorption amount for 60%, 80%, and 100% could be predicted as about 9702, 12,879, and 16,056 mg/kg, respectively. The largest amount of extracted P in the filter media with oyster shell after 30 days of P solution application was bound to Ca, followed by water soluble-P, Al-P, and Fe-P. Therefore, it was concluded that the adsorption amount of the phosphorus could be increased by adding the oyster shell to the filter medium. Also, it was concluded that adding the oyster shell to the filter medium in the constructed wetland was the scheme to extend the longevity of the constructed wetland by the phosphorus saturation, and using the oyster shell would be useful in aspect of economical efficiency and easiness. Especially, it would be the alternative proposal to reduce the environmental pollution in aspect of recycling wastes.     

The effect of pre-aeration on the purification processes in the long-term performance of a horizontal subsurface flow constructed wetland

Different conditions (water level, oxygen supply) prevailing in both beds of the Kodij?rve double-bed horizontal subsurface flow (HSSF) constructed wetland (CW) (Southern Estonia; constructed in 1996, total area 312.5 m(2), 40 pe) provide the opportunity to compare how different operational methods have altered the efficiency of the purification processes inside the HSSF CW. In summer 2002 a vertical subsurface flow (VSSF) CW (total area 37.4 m(2)) was added as the first stage of the system. Data from 18 sampling wells installed in Kodij?rve HSSF CW from two periods is compared: 1st period -- January 2000-April 2002 (before the VSSF CW was built); 2nd period --October 2002-December 2004 (after the construction of the VSSF filter). The VSSF CW has remarkably improved aerobic conditions in both beds of the HSSF. Apart from total phosphorus concentrations in the right bed and nitrate nitrogen concentrations in the outflow of both beds, all of the water quality indicators (dissolved oxygen, total suspended solids, biological oxygen demand, ammonia nitrogen, nitrite nitrogen, total nitrogen and total iron) improved after the construction of the VSSF filter. Typically, purification processes in the HSSF CW were dependent on oxygen supply, which was partly influenced by the water level inside the filter beds.     

The persistence and removal of enteric pathogens in constructed wetlands

Sedimentation is thought to be one of the mechanisms of microbial reduction from wetlands used for wastewater treatment. This study compared the occurrence and survival of enteric indicator microorganisms and pathogens in the water column and sediments of two constructed surface flow wetlands in Arizona. On a volume/wet weight basis the concentration of fecal coliforms and coliphage in the water column and sediment was similar. However, on a volume/dry weight basis the numbers were one to two orders of magnitude higher in the sediment. Giardia cyst and Cryptosporidium oocyst concentrations were one to three orders of magnitude greater in the sediment compared to the water column. The die-off rates of all the bacteria and coliphage were greater in the water column than the sediment. The die-off rates of fecal coliforms in the water and sediment were 0.256log(10)day(-1) and 0.151log(10)day(-1), respectively. The die-off rates of Salmonella typhimurium in the water and sediment were 0.345log(10)day(-1) and 0.312log(10)day(-1), respectively. The die-off rates of naturally occurring coliphage in water column and sediment were 0.397log(10)day(-1) and 0.107log(10)day(-1), respectively, and the die-off rates of and PRD-1 in water and sediment were 0.198log(10)day(-1) and 0.054log(10)day(-1), respectively. In contrast Giardia die-off in the sediment was greater compared to the water column. The die-off rates of Giardia in water and sediment were 0.029log(10)day(-1) and 0.37log(10)day(-1), respectively. Coliphage survived the longest of any group of organisms in the sediment and the least in the water column. In contrast Giardia survived best in the water column and least in the sediment.     

Constructed wetland systems vegetated with different plants applied to the treatment of tannery wastewater

Wastewaters from leather processing are very complex and lead to water pollution if discharged untreated, especially due to its high organic loading. In this study the survival of different plant species in subsurface horizontal flow constructed wetlands receiving tannery wastewater was investigated. Five pilot units were vegetated with Canna indica, Typha latifolia, Phragmites australis, Stenotaphrum secundatum and Iris pseudacorus, and a sixth unit was left as an unvegetated control. The treatment performance of the systems under two different hydraulic loading rates, 3 and 6 cmd(-1), was assessed. COD was reduced by 41-73% for an inlet organic loading varying between 332 and 1602 kgha(-1)d(-1) and BOD(5) was reduced by 41-58% for an inlet organic loading varying between 218 and 780 kgha(-1)d(-1). Nutrient removal occurred to lower extents. Phragmites australis and Typha latifolia were the only plants that were able to establish successfully. Despite the high removal of organic content from the influent wastewater, during 17 months of operation, no significant differences in performance were observed between units.     

Sorption of ionized and neutral emerging trace organic compounds onto activated sludge from different wastewater treatment configurations

The objective of this study was to examine sorption of a suite of 19 trace organic contaminants (TOrCs) to activated sludge. Compounds examined in this study included neutral, nonionized TOrCs as well as acidic TOrCs which may carry a negative charge and basic TOrCs which may carry a positive charge at the pH of wastewater. These TOrCs were evaluated to examine how sorptive behavior might differ for TOrCs in different states of charge. Additionally, multiple sludges from geographically and operationally different wastewater treatment plants were studied to elicit how solid-phase characteristics influence TOrC sorption. Characterization of sludge solids from 6 full scale treatment facilities and 3 bench-scale reactors showed no significant difference in fraction organic carbon (f_oc) and cation exchange capacity (CEC). Sorption experiments demonstrated that sorption of TOrCs also exhibits little variation between these different sludges. Organic carbon normalized partition coefficients (log K_oc) were determined as a measure of sorption, and were found to correlate well with octanol-water partition coefficients (log K_ow) for nonionized TOrCs, and log D_ow for anionic TOrCs where log D_ow is greater than 2. These data were used to construct a linear free energy relationship (LFER), which was comparable to existing LFERs for sorption onto sludge. No trend in sorption was apparent for the remaining anionic TOrCs or for the cationic TOrCs. These data suggest that predicting sorption to activated sludge based on K_ow values is a reasonable approach for neutral TOrCs using existing LFERs, but electrostatic (and likely other) interactions may govern the sorptive behavior of the charged organic chemicals to sludge.     

Removal of 1,4-dioxane from water using sonication: effect of adding oxidants on the degradation kinetics

This research investigates the effect of adding oxidants such as Fe0, Fe2+ and S2O8(2-) in the sonication of 1,4-dioxane (1,4-D). The results indicate that the degradation pattern of 1,4-D kinetically could be divided into three steps (initiation, acceleration, and stabilization), with the first two steps predominating. The initiation step agreed with zero order rate model, while the acceleration step was the pseudo-first order. In the presence of HCO3- as a radical scavenger, the degradations of 1,4-D and TOC were suppressed, indicating that OH radical is an important factor in the sonolysis, especially at the acceleration step. The overall degradation efficiency of 79.0% in the sonolysis of 1,4-D was achieved within 200 min. While Fe0, Fe2+ and S2O8(2-) were individually combined with sonication, the total degradation efficiency of 1,4-D increased 18.6%, 19.1% and 16.5% after 200 min, respectively. The addition of oxidants not only increased the rate constant in the acceleration step, but also changed the kinetic model from zero to pseudo-first order at the initiation step. The addition of oxidants such as Fe2+, Fe0 and S2O8(2-) in the sonication of 1,4-D also improved the mineralization of 1,4-D. However, the degradation efficiencies of 1,4-D and TOC were not statistically different (p = 0.709, ANOVA) with different oxidants such as Fe2+, Fe0 and S2O8(2-).     

Halophyte filter beds for treatment of saline wastewater from aquaculture

The expansion of aquaculture and the recent development of more intensive land-based marine farms require efficient and cost-effective systems for treatment of highly nutrient-rich saline wastewater. Constructed wetlands with halophytic plants offer the potential for waste-stream treatment combined with production of valuable secondary plant crops. Pilot wetland filter beds, constructed in triplicate and planted with the saltmarsh plant Salicornia europaea, were evaluated over 88 days under commercial operating conditions on a marine fish and shrimp farm. Nitrogen waste was primarily in the form of dissolved inorganic nitrogen (TDIN) and was removed by 98.2 ± 2.2% under ambient loadings of 109-383 μmol l⁻¹. There was a linear relationship between TDIN uptake and loading over the range of inputs tested. At peak loadings of up to 8185 ± 590 μmol l⁻¹ (equivalent to 600 mmol N m⁻² d⁻¹), the filter beds removed between 30 and 58% (250 mmol N m⁻² d⁻¹) of influent TDIN. Influent dissolved inorganic phosphorus levels ranged from 34 to 90 μmol l⁻¹, with 36-89% reduction under routine operations. Dissolved organic nitrogen (DON) loadings were lower (11-144 μmol l⁻¹), and between 23 and 69% of influent DON was removed during routine operation, with no significant removal of DON under high TDIN loading. Over the 88-day study, cumulative nitrogen removal was 1.28 mol m⁻², of which 1.09 mol m⁻² was retained in plant tissue, with plant uptake ranging from 2.4 to 27.0 mmol N g⁻¹ dry weight d⁻¹. The results demonstrate the effectiveness of N and P removal from wastewater from land-based intensive marine aquaculture farms by constructed wetlands planted with S. europaea.     

The management of undesirable cyanobacteria blooms in channel catfish ponds using a constructed wetland: Contribution to the control of off-flavor occurrences

An exploratory study on the management of undesirable cyanobacteria blooms with respect to off-flavor problems using an integrated vertical-flow constructed wetland (CW) was performed at a small commercial-scale channel catfish farm from 2004 to 2007. The results of the three-year experiment indicated that water treatment by the CW could reduce the possibility of dominance by undesirable cyanobacteria species that often cause off-flavor problems. A detailed investigation in 2007, showed that the concentrations of geosmin, MIB (2-methylisoborneol), and β-cyclocitral in the water of the recirculating pond (4.3 ng L⁻¹, U.D. (undetected) and 0.2 ng L⁻¹, respectively) treated by the CW were significantly lower than those in the control pond (152.6 ng L⁻¹, 63.3 ng L⁻¹ and 254.8 ng L⁻¹, respectively). In addition, the relationships among the cyanobacteria species, the off-flavor compounds and ten environmental variables were explored by canonical correspondence analysis (CCA). The results showed that Oscillatoria sp., Oscillatoria kawamurae and Microcystis aeruginosa were the main sources of off-flavor compounds in the catfish ponds. The successful manipulation of undesirable cyanobacteria species potentially resulted in lower concentrations of odorous compounds in the water of the recirculating pond. An investigation of the concentrations of geosmin and MIB in catfish fillets showed that the levels of odorous compounds were below the OTC (odor threshold concentration) values in the recirculating pond but were above the OTC values from July to October in the control pond. Water recycling by the CW could potentially be one of the best management practices to control off-flavor occurrences in aquaculture.     

Application of the self-organizing map (SOM) to assess the heavy metal removal performance in experimental constructed wetlands

The self-organizing map (SOM) model was applied to elucidate heavy metal removal mechanisms and to predict heavy metal concentrations in experimental constructed wetlands treating urban runoff. A newly developed SOM map showed that nickel in constructed wetland filters is likely to leach under high conductivity in combination with low pH in winter. In contrast, influent pH and conductivity were not shown to have clear relationships with copper (Cu) concentrations in the effluent, suggesting that the mobility of Cu was not considerably affected by salt increase during winter. The accuracy of prediction with SOM was highly satisfactory, suggesting heavy metals can be efficiently estimated by applying the SOM model with input variables such as conductivity, pH, temperature and redox potential, which can be monitored in real time. Moreover, domain understanding was not required to implement the SOM model for prediction of heavy metal removal efficiencies.     

Evaluation of the metabolic diversity of microbial communities in four different filter layers of a constructed wetland with vertical flow by Biolog™ analysis

The community-level substrate utilization test based on direct incubation of environmental samples in Biolog EcoPlates™ is a suitable and sensitive tool to characterize microbial communities. The aim of this study was to investigate the influence of plant roots and soil structure on the metabolic diversity of microorganisms in a constructed wetland with vertical flow.Sediment samples were taken from different filter depths representing specific filter layers. The color development representing the substrate utilization was measured with the samples over a period of 10 days. The average well color development (AWCD) for all carbon sources was calculated as an indicator of total activity and in order to compensate the influence of the inoculum's density on the color development in the plates. After transformation by dividing by the AWCD, the optical density data were analysed by principal component analysis (PCA). An analysis of the kinetic profile of the AWCD was carried out to increase the analytical power of the method. The corrected data have been successfully fit to the logistic growth equation. Three kinetic model parameters, the asymptote (K), the exponential rate of color change (p) and the time to the midpoint of the exponential portion of the curve (s), were used for statistical analysis of the physiological profile of the microbial community in the different filter layers of the constructed wetland.We found out that in the upper two horizons, which were rooted most densely, mainly easily degradable materials like specific carbohydrates were utilized, while in the lower layers, where only single roots occur, more biochemically inert compounds, e.g. 2-hydroxy benzoic acid, were utilized. Furthermore it could be shown that microorganisms in the surface layer benefited from the plant litter because they can utilize decay products of these. In the lower filter layers specialists took advantage because they had to cope with the biochemically inert materials and the lower nutrient supply.     

Sulphate reduction and the removal of carbon and ammonia in a laboratory-scale constructed wetland

Sulphate is a normal constituent of domestic wastewater and reduced sulphur compounds are known to be potent inhibitors of plant growth and certain microbial activities. However, the knowledge about sulphate reduction and the effect on the removal of C and N in constructed wetlands is still limited. Investigations in laboratory-scale constructed wetland reactors were performed to evaluate the interrelation of carbon and nitrogen removal with the sulphate reduction by use of artificial domestic wastewater. Carbon removal was found to be only slightly affected and remained at high levels of efficiency (75-90%). Only at sulphate reduction intensities above 75 mgl(-1) (50% removal), a decrease of carbon removal of up to 20% was observed. A highly contrary behaviour of ammonia removal was found in general, which decreased exponentially from 75% to 35% related to a linear increase of sulphate reduction up to 75 mgl(-1) (50% removal). Since sulphate removal is considered to be dependant on the load of electron donors, the carbon load of the system was varied. Variation of the load changed the intensities of sulphate reduction immediately, but did not influence the carbon removal effectiveness. Doubling of the carbon concentration of 200 mgl(-1) BOD(5) for domestic wastewater usually led to sulphate reduction of up to 150 mgl(-1) (100% removal). The findings show that, particularly in constructed wetland systems, the sulphur cycle in the rhizosphere is of high importance for performance of the waste water treatment and may initiate a reconsideration of the amount of sulphate present in the tap water systems.     

Seasonal influence on sulfate reduction and zinc sequestration in subsurface treatment wetlands

To characterize the effects of season, temperature, plant species, and chemical oxygen demand (COD) loading on sulfate reduction and metals removal in treatment wetlands we measured pore water redox potentials and concentrations of sulfate, sulfide, zinc and COD in subsurface wetland microcosms. Two batch incubations of 20 day duration were conducted in each of four seasons defined by temperature and daylight duration. Four treatments were compared: unplanted controls, Typha latifolia (broadleaf cattail), and Schoenoplectus acutus (hardstem bulrush), all at low COD loading (267 mg/L), plus bulrush at high COD loading (534 mg/L). Initial SO4-S and zinc concentrations were 67 and 24 mg/L, respectively. For all treatments, sulfate removal was least in winter (4 degrees C, plant dormancy) greatest in summer (24 degrees C, active plant growth) and intermediate in spring and fall (14 degrees C), but seasonal variation was greater in cattail, and especially, bulrush treatments. Redox measurements indicated that, in winter, plant-mediated oxygen transfer inhibited activity of sulfate reducing bacteria, exacerbating the reduction in sulfate removal due to temperature. Doubling the COD load in bulrush treatments increased sulfate removal by only 20-30% when averaged over all seasons and did not alter the basic pattern of seasonal variation, despite tempering the wintertime increase in redox potential. Seasonal and treatment effects on zinc removal were broadly consistent with sulfate removal and presumably reflected zinc-sulfide precipitation. Results strongly suggest that interactive effects of COD loading rate, temperature, season, and plant species control not only sulfate reduction and zinc sequestration, but also the balance of competition between various microbial consortia responsible for water treatment in constructed wetlands.     

Evaluation of the mechanisms of the effect of ultrasound on Microcystis aeruginosa at different ultrasonic frequencies

Blooms of cyanobacteria are now considered to be a common environmental issue. They are hazardous to both domestic and wild animals and humans. Current treatments are unable to effectively control such blooms as they become tolerant to biocides and it is difficult to degrade cyanobacterial toxins in water. Alternative methods for control are currently under investigation. One potential effective method is ultrasonic irradiation. Ultrasound inactivates algal and cyanobacteria cells through cavitation by generating extreme conditions, resulting in a number of physical, mechanical and chemical effects. The aim of this study was to investigate the effect of ultrasound at different frequencies on Microcystis aeruginosa. Flow cytometry was used to measure cyanobacterial metabolic cell viability in addition to the more commonly used haemocytometry, optical density and fluorimetry. Results indicate low frequency 20 kHz ultrasound with high intensity (0.0403 W cm⁻³) is effective for the inactivation of cyanobacterial cells. Higher frequencies of 580 kHz (0.0041 W cm⁻³) also resulted in an inactivation effect, but 1146 kHz (0.0018 W cm⁻³) showed a declumping effect as evidenced by flow cytometry. Ultrasonic treatment over time under different sonication conditions demonstrates the following:1. Acoustic cavitation via mechanical effects can induce sufficient shear forces to directly rupture cyanobacteria cells.2. At higher ultrasonic frequencies the mechanical energy of cavitation is less but a larger proportion of free radicals are produced from the ultrasonic degradation of water, which chemically attacks and weakens the cyanobacteria cell walls.3. At higher frequencies free radicals also damage chlorophyll a leading to a loss in photosynthetic cell viability.4. At low powers ultrasonic energy results in declumping of cyanobacteria.     

Dynamics of sulphur compounds in horizontal sub-surface flow laboratory-scale constructed wetlands treating artificial sewage

The knowledge regarding the dynamics of sulphur compounds inside constructed wetlands is still insufficient. Experiments in planted (Juncus effusus) and unplanted horizontal sub-surface-flow laboratory-scale constructed wetlands fed with artificial wastewater were carried out to evaluate the sulphate reduction, the composition and dynamics of generated sulphur compounds, as well as the influence of carbon load and plants on processes of sulphur transformation.In planted and unplanted wetlands, the addition of organic carbon (TOC of about 120 mg L⁻¹) immediately affected the transformation of up to 90% of the incoming sulphate (150 mg L⁻¹), directing it mainly towards elemental sulphur (30%) and sulphide (8%). During this experimental period, nearly 52% of the transformed sulphate-sulphur was calculated to be immobilized inside the planted wetland and 66% inside the unplanted one.In subsequent experiments, the deficiency of organic carbon inside the planted wetlands favoured the decrease of elemental sulphur in the pore water coupled to retransformation of depot-sulphur to dissolved sulphate. Nearly 90% of the deposited and reduced sulphur was found to be reoxidized. In principle, the results indicate a substantial improvement of this reoxidation of sulphur by oxygen released by the helophytes. Surplus of organic carbon promotes the ongoing sulphate reduction and the stability of deposed and dissolved reduced sulphur compounds.In contrast, inside the unplanted control wetland, a relative stability of the formed sulphur depots and the generated amount of dissolved sulphur compounds including elemental sulphur could be observed independently of the different loading conditions.     

Effect of precursor concentration on the characteristics of nanoscale zerovalent iron and its reactivity of nitrate

Differing precursor concentrations, 1.0, 0.1, and 0.01 M FeCl(3) x 6H(2)O, were performed to produce nanoscale Fe(0) and the results were discussed in terms of the specific surface area, particle size and electrochemical properties. The results indicated that the nanoscale Fe(0) prepared by 0.01 M FeCl(3) had absolutely reduced in size (9-10nm) and possessed the greatest specific surface area (56.67 m(2) g(-1)). These synthesized nanoscale Fe(0) particles were attempted to enhance the removal of 40 mg-NL(-1) unbuffered nitrate solution. The first-order degradation rate constants (k(obs)) increased significantly (5.5-8.6 times) with nanoscale Fe(0) prepared by 0.01 M precursor solution (Fe(0.01 M)(0)). When normalized to iron surface area concentration, the specific rate constant (k(SA)) was increased by a factor of approximately 1.7-2.4 using Fe(0.01 M)(0) (6.84 x 10(-4) L min(-1) m(-2) for Fe(0.01 M)(0), 4.04 x 10(-4) L min(-1) m(-2) for Fe(0.1 M)(0) and 2.80 x 10(-4) L min(-1) m(-2) for Fe(1 M)(0)). The rise of reactivity of the reactive site on the Fe(0.01 M)(0) surface was indicated by the specific rate constant (k(SA)) calculation and the i(0) value of the electrochemical test.     

Phosphorus removal using Ca-rich hydrated oil shale ash as filter material - The effect of different phosphorus loadings and wastewater compositions

We studied the phosphorus (P) binding capacity of Ca-rich alkaline filter material - hydrated oil shale ash (i.e. hydrated ash) in two onsite pilot-scale experiments (with subsurface flow filters) in Estonia: one using pre-treated municipal wastewater with total phosphorus (TP) concentration of 0.13-17.0 mg L⁻¹ over a period of 6 months, another using pre-treated landfill leachate (median TP 3.4 mg L⁻¹) for a total of 12 months. The results show efficient P removal (median removal of phosphates 99%) in horizontal flow (HF) filters at both sites regardless of variable concentrations of several inhibitors. The P removal efficiency of the hydrated ash increases with increasing P loading, suggesting direct precipitation of Ca-phosphate phases rather than an adsorption mechanism. Changes in the composition of the hydrated ash suggest a significant increase in P concentration in all filters (e.g. from 489.5 mg kg⁻¹ in initial ash to 664.9 mg kg⁻¹ in the HF filter after one year in operation), whereas almost all TP was removed from the inflow leachate (R² = 0.99). Efficiency was high throughout the experiments (median outflow from HF hydrated ash filters 0.05-0.50 mg L⁻¹), and P accumulation did not show any signs of saturation.