Pilot-scale investigation on the removal of organic foulants in secondary effluent by slow sand filtration prior to ultrafiltration

Natural biofiltration processes have been verified as effective pre-treatment choice improving the performance of low-pressure membranes (MF/UF) in wastewater reclamation. In the present work, pilot-scale slow sand filtration (SSF) was used to simulate bank filtration at high filtration rates (from 0.25 m/h to 0.5 m/h) to filter secondary effluent prior to UF. The results showed that SSF improved the performance of UF to a large extent. Related to previous work biopolymers are considered as major dissolved organic foulants in treated wastewater. The removal of these organic foulants in slow sand filters and factors affecting the performance of SSF were investigated. It was observed that the removal of biopolymers took place mainly at the upper sand layer and was related to biological degradation. Tests on the degradability of biopolymers verified that they are biodegradable. Sixteen months monitoring of biopolymer concentration in the secondary effluent indicated that it varied seasonally. In winter season the concentration was much higher than during the summer months. Higher temperature and lower biopolymer concentration led to more effective foulants removal and more sustainable operation of SSF. During the whole experimental period, the performance of SSF was always better at filtration rate of 0.25 m/h than at 0.5 m/h. Under the present experimental conditions, SSF exhibited stable and effective biopolymer removal at temperatures higher than 15 °C, at biopolymer concentrations lower than 0.5 mg C/L and with sufficient oxygen available.     

Transport and fate of Cryptosporidium parvum oocysts in intermittent sand filters.

The transport potential of Cryptosporidium parvum (C. parvum) through intermittent, unsaturated, sand filters used for water and wastewater treatment was investigated using a duplicated, 2³ factorial design experiment performed in bench-scale, sand columns. Sixteen columns (dia=15 cm, L=60 cm) were dosed eight times daily for up to 61 days with 65,000 C. parvum oocysts per liter at 15°C. The effects of water quality, media grain size, and hydraulic loading rates were examined. Effluent samples were tested for pH, turbidity, and oocyst content. C. parvum effluent concentrations were determined by staining oocysts on polycarbonate filters and enumerating using epifluorescent microscopy. At completion, the columns were dismantled and sand samples were taken at discrete depths within the columns. These samples were washed in a surfactant solution and the oocysts were enumerated using immunomagnetic separation techniques.

The fine-grained sand columns (d₅₀=0.31 mm) effectively removed oocysts under the variety of conditions examined with low concentrations of oocysts infrequently detected in the effluent. Coarse-grained media columns (d₅₀=1.40 mm) yielded larger numbers of oocysts which were commonly observed in the effluent regardless of operating conditions. Factorial design analysis indicated that grain size was the variable which most affected the oocyst effluent concentrations in these intermittent filters. Loading rate had a significant effect when coarse-grained media was used and lesser effect with fine-grained media while the effect of feed composition was inconclusive. No correlations between turbidity, pH, and effluent oocyst concentrations were found. Pore-size calculations indicated that adequate space for oocyst transport existed in the filters. It was therefore concluded that processes other than physical straining mechanisms are mainly responsible for the removal of C. parvum oocysts from aqueous fluids in intermittent sand filters used under the conditions studied in this research.     

Transport and fate of Cryptosporidium parvum oocysts in intermittent sand filters

The transport potential of Cryptosporidium parvum (C. parvum) through intermittent, unsaturated, sand filters used for water and wastewater treatment was investigated using a duplicated, 2³ factorial design experiment performed in bench-scale, sand columns. Sixteen columns (dia=15 cm, L=60 cm) were dosed eight times daily for up to 61 days with 65,000 C. parvum oocysts per liter at 15°C. The effects of water quality, media grain size, and hydraulic loading rates were examined. Effluent samples were tested for pH, turbidity, and oocyst content. C. parvum effluent concentrations were determined by staining oocysts on polycarbonate filters and enumerating using epifluorescent microscopy. At completion, the columns were dismantled and sand samples were taken at discrete depths within the columns. These samples were washed in a surfactant solution and the oocysts were enumerated using immunomagnetic separation techniques.The fine-grained sand columns (d₅₀=0.31 mm) effectively removed oocysts under the variety of conditions examined with low concentrations of oocysts infrequently detected in the effluent. Coarse-grained media columns (d₅₀=1.40 mm) yielded larger numbers of oocysts which were commonly observed in the effluent regardless of operating conditions. Factorial design analysis indicated that grain size was the variable which most affected the oocyst effluent concentrations in these intermittent filters. Loading rate had a significant effect when coarse-grained media was used and lesser effect with fine-grained media while the effect of feed composition was inconclusive. No correlations between turbidity, pH, and effluent oocyst concentrations were found. Pore-size calculations indicated that adequate space for oocyst transport existed in the filters. It was therefore concluded that processes other than physical straining mechanisms are mainly responsible for the removal of C. parvum oocysts from aqueous fluids in intermittent sand filters used under the conditions studied in this research.     

Bacterial, viral and turbidity removal by intermittent slow sand filtration for household use in developing countries: experimental investigation and modeling

A two-factor three-block experimental design was developed to permit rigorous evaluation and modeling of the main effects and interactions of sand size (d₁₀ of 0.17 and 0.52 mm) and hydraulic head (10, 20, and 30 cm) on removal of fecal coliform (FC) bacteria, MS2 bacteriophage virus, and turbidity, under two batch operating modes (‘long’ and ‘short’) in intermittent slow sand filters (ISSFs). Long operation involved an overnight pause time between feeding of two successive 20 L batches (16 h average batch residence time (RT)). Short operation involved no pause between two 20 L batch feeds (5 h average batch RT). Conditions tested were representative of those encountered in developing country field settings. Over a ten week period, the 18 experimental filters were fed river water augmented with wastewater (influent turbidity of 5.4-58.6 NTU) and maintained with the wet harrowing method. Linear mixed modeling allowed systematic estimates of the independent marginal effects of each independent variable on each performance outcome of interest while controlling for the effects of variations in a batch’s actual residence time, days since maintenance, and influent turbidity. This is the first study in which simultaneous measurement of bacteria, viruses and turbidity removal at the batch level over an extended duration has been undertaken with a large number of replicate units to permit rigorous modeling of ISSF performance variability within and across a range of likely filter design configurations and operating conditions.On average, the experimental filters removed 1.40 log fecal coliform CFU (SD 0.40 log, N = 249), 0.54 log MS2 PFU (SD 0.42 log, N = 245) and 89.0 percent turbidity (SD 6.9 percent, N = 263). Effluent turbidity averaged 1.24 NTU (SD 0.53 NTU, N = 263) and always remained below 3 NTU. Under the best performing design configuration and operating mode (fine sand, 10 cm head, long operation, initial HLR of 0.01-0.03 m/h), mean 1.82 log removal of bacteria (98.5%) and mean 0.94 log removal of MS2 viruses (88.5%) were achieved.Results point to new recommendations regarding filter design, manufacture, and operation for implementing ISSFs in local settings in developing countries. Sand size emerged as a critical design factor on performance. A single layer of river sand used in this investigation demonstrated removals comparable to those reported for 2 layers of crushed sand. Pause time and increased residence time each emerged as highly beneficial for improving removal performance on all four outcomes. A relatively large and significant negative effect of influent turbidity on MS2 viral removal in the ISSF was measured in parallel with a much smaller weaker positive effect of influent turbidity on FC bacterial removal. Disturbance of the schmutzdecke by wet harrowing showed no effect on virus removal and a modest reductive effect on the bacterial and turbidity removal as measured 7 days or more after the disturbance. For existing coarse sand ISSFs, this research indicates that a reduction in batch feed volume, effectively reducing the operating head and increasing the pore:batch volume ratio, could improve their removal performance by increasing batch residence time.     

Impact of population and latrines on fecal contamination of ponds in rural Bangladesh

A majority of households in Bangladesh rely on pond water for hygiene. Exposure to pond water fecal contamination could therefore still contribute to diarrheal disease despite the installation of numerous tubewells for drinking. The objectives of this study are to determine the predominant sources (human or livestock) of fecal pollution in ponds and examine the association between local population, latrine density, latrine quality and concentrations of fecal bacteria and pathogens in pond water. Forty-three ponds were analyzed for E. coli using culture-based methods and E. coli, Bacteroidales and adenovirus using quantitative PCR. Population and sanitation spatial data were collected and measured against pond fecal contamination. Humans were the dominant source of fecal contamination in 79% of the ponds according to Bacteroidales measurements. Ponds directly receiving latrine effluent had the highest concentrations of fecal indicator bacteria (up to 10⁶ Most Probable Number (MPN) of culturable E. coli per 100 mL). Concentrations of fecal indicator bacteria correlated with population surveyed within a distance of 30-70 m (p < 0.05) and total latrines surveyed within 50-70 m (p < 0.05). Unsanitary latrines (visible effluent or open pits) within the pond drainage basin were also significantly correlated to fecal indicator concentrations (p < 0.05). Water in the vast majority of the surveyed ponds contained unsafe levels of fecal contamination attributable primarily to unsanitary latrines, and to lesser extent, to sanitary latrines and cattle. Since the majority of fecal pollution is derived from human waste, continued use of pond water could help explain the persistence of diarrheal disease in rural South Asia.     

Comparing steroid estrogen, and nonylphenol content across a range of European sewage plants with different treatment and management practices

The effluent of 17 sewage treatment works (STW) across Norway, Sweden, Finland, The Netherlands, Belgium, Germany, France and Switzerland was studied for the presence of estradiol (E2), estrone (E1), ethinylestradiol (EE2) and nonylphenol (NP). Treatment processes included primary and chemical treatment only, submerged aerated filter, oxidation ditch, activated sludge (AS) and combined trickling filter with activated sludge. The effluent strength ranged between 87 and 846 L/PE (population equivalent), the total hydraulic retention time (HRT) ranged between 4 and 120 h, sludge retention time (SRT) between 3 and 30 d, and water temperature ranged from 12 to 21 °C. The highest estrogen values were detected in the effluent of the STW which only used primary treatment (13 ng/L E2 and 35 ng/L E1) and on one occasion in one of the STW using the AS system (6.5 ng/L E2, 50.5 ng/L E1, but on three other occasions the concentrations in this STW were at least a factor of 6 lower). For the 16 STW employing secondary treatment E2 was only detected in the effluent of six works during the study period (average 0.7-5.7 ng/L). E1 was detected in the effluent of 13 of the same STW. The median value for E1 for the 16 STW with secondary treatment was 3.0 ng/L. EE2 was only detected in two STW (1.1, <0.8-2.8 ng/L). NP could be detected in the effluent of all 14 STW where this measurement was attempted, with a median of 0.31 μg/L and values ranging from 0.05 to 1.31 μg/L. A comparison of removal performance for E1 was carried out following prediction of the probable influent concentration. A weak but significant (α<5%) correlation between E1 removal and HRT or SRT was observed.     

Bacterial treatment effectiveness of point-of-use ceramic water filters

Laboratory experiments were conducted on six point-of-use (POU) ceramic water filters that were manufactured in Nicaragua; two filters were used by families for ca. 4 years and the other filters had limited prior use in our lab. Water spiked with ca. 10⁶ CFU/mL of Escherichia coli was dosed to the filters. Initial disinfection efficiencies ranged from 3 - 4.5 log, but the treatment efficiency decreased with subsequent batches of spiked water. Silver concentrations in the effluent water ranged from 0.04 - 1.75 ppb. Subsequent experiments that utilized feed water without a bacterial spike yielded 10³-10⁵ CFU/mL bacteria in the effluent. Immediately after recoating four of the filters with a colloidal silver solution, the effluent silver concentrations increased to 36 - 45 ppb and bacterial disinfection efficiencies were 3.8-4.5 log. The treatment effectiveness decreased to 0.2 - 2.5 log after loading multiple batches of highly contaminated water. In subsequent loading of clean water, the effluent water contained <20-41 CFU/mL in two of the filters. This indicates that the silver had some benefit to reducing bacterial contamination by the filter. In general these POU filters were found to be effective, but showed loss of effectiveness with time and indicated a release of microbes into subsequent volumes of water passed through the system.     

Intermittent filtration of wastewater--removal of fecal coliforms and fecal streptococci

Removal of fecal coliforms and fecal streptococci was monitored over a period of 13 months in 14 buried pilot scale filters, treating septic tank effluent. The effects of grain size, hydraulic dosing rate and distribution method were investigated. Two different natural sands (sorted sand and unsorted sand) and three different types of light weight aggregates (LWA 0-4 mm, LWA 2-4 mm and crushed LWA 0-3 mm) were used. Intermittent dosing rates from 20 to 80 mm/day in 12 doses per day were applied to the filters by uniform pressure distribution or point application by gravity dosing. Removal of fecal coliforms was more than three orders of magnitude higher in the media with the finest grain sizes (unsorted sand) as compared to the coarsest media (LWA 0-4 mm and LWA 2-4 mm) operated under same conditions. Fecal streptococci were determined only in effluent from filters with LWA 0-4 mm and LWA 2-4 mm. Higher removal of fecal coliforms was observed in pressure dosed filters compared to gravity dosed filters. A lower removal was observed by increasing the hydraulic dosing rate. Minimum retention time was found to be a key parameter for predicting removal of bacteria in unsaturated, aerobic filters. At minimum retention times lower than about 50 h, there was a correlation of 0.96 between retention time and removal of fecal coliforms. Retention times longer than 50 h gave almost complete removal of fecal coliforms.     

Impact of ozonation on ecotoxicity and endocrine activity of tertiary treated wastewater effluent

Tertiary wastewater treatment plant effluent before and after ozonation (0.6-1.1 g O₃/g DOC) was tested for aquatic ecotoxicity in a battery of standardised microbioassays with green algae, daphnids, and zebrafish eggs. In addition, unconjugated estrogen and 17β-hydroxyandrogen immunoreactive substances were quantified by means of enzyme immunoassays, and endocrine effects were analysed in a 21-day fish screening assay with adult male and female medaka (Oryzias latipes). Ozonation decreased estrogen-immunoreactivity by 97.7 ± 1.2% and, to a lesser extent, androgen-immunoreactivity by 56.3 ± 16.5%. None of the short-term exposure ecotoxicity tests revealed any adverse effects of the tertiary effluent, neither before nor after the ozonation step. Similarly in the fish screening assay, reproductive fitness parameters showed no effects attributed to micropollutants, and no detrimental effects of the effluents were observed. Based on the presented screening, ozonation effectively reduced steroid hormone levels in the wastewater treatment plant effluent without increasing the effluent's ecotoxicity.     

Biofiltration of wastewater treatment plant effluent: effective removal of pharmaceuticals and personal care products and reduction of toxicity

This study investigates biofiltration for the removal of dissolved organic carbon (DOC), pharmaceuticals and personal care products (PPCPs), and for the reduction of non-specific toxicity expressed as baseline toxicity equivalent concentration (baseline-TEQ). Two filtering media, sand and granular activated carbon, were tested. The influence of pre-ozonation and empty-bed contact time (EBCT, from 30 to 120 min) was determined. The experiments were performed at a pilot-scale with real WWTP effluent. A previous study showed that biological activity had developed on the filtering media and dissolved organic removal had reached a steady state before sampling commenced. The results show that biological activated carbon (BAC) has a good potential for the removal of DOC (35-60%), PPCPs (>90%) and baseline-TEQ (28-68%) even without pre-ozonation. On the contrary, the sand shows limited improvement of effluent quality. Varying the EBCT does not influence the performance of the BAC filters; however, dissolved oxygen concentration could be a limiting factor. The performances of the BAC filters were stable for over two years suggesting that the main mechanism of organic matter and PPCPs removal is biodegradation. It is concluded that BAC filtration without pre-ozonation could be implemented as a low cost advanced treatment option to improve WWTP effluent chemical quality.     

Application of high rate nitrifying trickling filters for potable water treatment

The interference of ammonia with chlorination is a prevalent problem encountered by water treatment plants located throughout South East Asia. The efficacy of high rate, plastic-packed trickling filters as a pre-treatment process to remove low concentrations of ammonia from polluted surface water was investigated. This paper presents the findings from a series of pilot experiments, which were designed to investigate the effect of specific conditions—namely low ammonia feed concentrations (0.5-5.0 mg NH₄-N L⁻¹), variations in hydraulic surface load (72.5-145 m³ m⁻² d⁻¹) and high suspended solid loads (51 ± 25 mg L⁻¹)—on filter nitrifying capacity. The distribution of nitrification activity throughout a trickling filter bed was also characterised. Results confirmed that high hydraulic rate trickling filters were able to operate successfully, under ammonia-N concentrations some 10- to 50-fold lower and at hydraulic loading rates 30-100 times greater than those of conventional wastewater applications. Mass transport limitations posed by low ammonia-N concentrations on overall filter performance were insignificant, where apparent nitrification rates (0.4-1.6 g NH₄-N m⁻² d⁻¹), equivalent to that of wastewater filters were recorded. High inert suspended solid loadings had no adverse effect on nitrification. Results imply that implementation of high rate trickling filters at the front-end of a water treatment train would reduce the ammonia-related chlorine demand, thereby offering significant cost savings.     

Analysis of environmental endocrine disrupting chemicals using the E-screen method and stir bar sorptive extraction in wastewater treatment plant effluents

Endocrine disrupting chemicals (EDCs) have become a major issue in the field of environmental science due to their ability to interfere with the endocrine system. Recent studies show that surface water is contaminated with EDCs, many released from wastewater treatment plants (WWTP). This pilot study used biological (E-screen assay) and chemical (stir bar sorptive extraction-GC-MS) analyses to quantify estrogenic activity in effluent water samples from a municipal WWTP and in water samples of the recipient river, upstream and downstream of the plant.The E-screen assay was performed on samples after solid phase extraction (SPE) to determine total estrogenic activity; the presence of estrogenic substances can be evaluated by measuring the 17-β-estradiol equivalency quantity (EEQ). Untreated samples were also assayed with an acute toxicity test (Vibrio fischeri) to study the correlation between toxicity and estrogenic disruption activity.Mean EEQs were 4.7 ng/L (± 2.7 ng/L) upstream and 4.4 ng/L (± 3.7 ng/L) downstream of the plant, and 11.1 ng/L (± 11.7 ng/L) in the effluent. In general the WWTP effluent had little impact on estrogenicity nor on the concentration of EDCs in the river water. The samples upstream and downstream of the plant were non-toxic or weakly toxic (0 < TU < 0.9) while the effluent was weakly toxic or toxic (0.4 < TU < 7.6). Toxicity and estrogenic activity were not correlated.At most sites, industrial mimics, such as the alkylphenols and phthalates, were present in higher concentrations than natural hormones. Although the concentrations of the detected xenoestrogens were generally higher than those of the steroids, they accounted for only a small fraction of the EEQ because of their low estrogenic potency. The EEQs resulting from the E-screen assay and those calculated from the results of chemical analyses using estradiol equivalency factors were comparable for all samples and closely correlated.     

Seawater induced algal flocculation

The effectiveness of the use of seawater in the removal of algae from oxidation pond effluents was investigated. Freshly collected samples of pond effluent were initially adjusted to pH levels of 9.0–11.5, then seawater in proportions of 0–20% (v/v) was added. The jar test technique was used to determine algal removal efficiencies. The effect of the process on alkalinity in the samples was studied.Test results indicated that the primary reactions responsible for the removal of algae were the formation and precipitation of CaCO₃ and Mg(OH)₂. These reactions were initiated at pH values of 9.5 and 11.0, respectively, in the absence of seawater. As seawater concentrations were increased, the reactions were initiated at lower pH values. Algal removals in excess of 80% were achieved at an initial pH of 10.5 and 5–10% seawater. Nearly complete removal (> 95%) was achieved at an initial pH of 11.0 and 10–15% seawater.     

Passive sampling combined with ecotoxicological and chemical analysis of pharmaceuticals and biocides - evaluation of three Chemcatcher™ configurations

Passive sampling is a tool to monitor the presence and concentrations of micropollutants in the aquatic environment. We investigated the duration of integrative sampling and the effects of flow rate on the performance of three configurations of the Chemcatcher - a sampler for polar organic compounds. Chemcatchers were fitted with Empore™ styrenedivinylbenzene (SDB) XC disks (XC), SDB-RPS disks (RPS) or SDB-RPS disks covered with a polyethersulfone membrane (RPS-PES). Samplers were either exposed to treated sewage effluent for 5 days at various flow rates, or at a single flow rate with overlapping exposures of 3-24 days. Chemical analysis focused on a set of pharmaceuticals and biocides and ecotoxicological analysis measured inhibition of photosystem II in algae. For compounds with log K_OW > 2, both XC and RPS disks respond dynamically to higher flow rates; uptake increased up to five-fold when flow increased from 0.03 to 0.37 m s⁻¹. At a flow rate of 0.13 m s⁻¹ the integrative window of SDB disks approached 6 days for more hydrophobic compounds (log K_OW > 3.5). The RPS-PES configuration was less affected by flow and also showed an extended integrative window (up to 24 days). The membrane causes a lag phase of up to 2.3 days which thwarts a sound interpretation of data from sampling periods of less than 10 days.     

Influence of sand layer depth and percolate impounding regime on nitrogen transformation in vertical-flow constructed wetlands treating faecal sludge

Four laboratory-scale units of vertical-flow constructed wetlands (VFCW) were fed once a week with faecal sludge (FS) at a constant solids loading rate (SLR) of 250 kg TS/(m².year) (equivalent to 260-300 g N/(m².week)) for a period of 12 weeks to study: i) the nitrification and denitrification potential of the sand layer of VFCWs and ii) the effect of percolate impounding regime (permanent or batch-impounding) on nitrogen transformation. The TN content of raw FS was characterised by 65% org-N, 34% NH₄-N and 1% NO_x-N. After FS application and a six-day impounding period, 8-13% TN were recovered in the percolate exhibiting the following composition: 70-80% NH₄-N, 25-30% org-N and <1% NO_x-N. A large fraction of the influent organic N (55%) was filtered in the bed and 24-29% of initial NH₄-N were lost due to nitrification and volatilisation. In permanent impounding systems, 8-11% TN were recovered in the percolate versus 13% in batch-operated beds. N loss was increased with sand layer depth (20-40 cm) under permanent impounding regimes.     

Strength enhancement of clay by encapsulating geogrids in thin layers of sand

Large size direct shear tests (i.e.300 × 300 × 200 mm) were conducted to investigate the possibility of strength enhancement of clays reinforced with geogrids embedded in thin layers of sand. In this paper test results for the clay, sand, clay–sand, clay–geogrid, sand–geogrid and clay–sand–geogrid samples are presented and discussed. Thin sand layers with thicknesses of 4, 6, 8, 10, 12 and 14 mm were used to quantify their effect on the interaction between the clay and the geogrids. In this regard effects of sand layer thickness, normal pressure (i.e. confinement) and transversal members of geogrids were investigated. All the tests were conducted using saturated clay with no drainage allowed. Test results indicate that provision of thin layers of sand for encapsulating the geogrids is very effective in improving the strength and deformation characteristics of saturated clay. Maximum strength enhancement was derived at an optimum sand layer thickness of 10 mm which proved to be independent of the magnitude of the normal pressure used. For a particular sand layer thickness, increasing the normal pressure resulted in enhanced strength improvement. Results also showed that removal of the geogrid transversal members resulted in reducing the strength of the reinforced samples by 10% compared to geogrids with transversal members. Encapsulating geogrids in thin layers of sand not only will improve the performance of clays if used as backfill it would also provide drainage paths preventing pore water pressure generation on saturation of the backfill.     

Transport and retention of a bacteriophage and microspheres in saturated, angular porous media: effects of ionic strength and grain size

Eight saturated column experiments were conducted to examine the effects of solution chemistry and grain size on the transport of colloids through crushed silica sand. Two sizes of colloids, 0.025-μm bacteriophage (MS-2) and 1.5-μm carboxylated microspheres, were used as surrogates for the transport of pathogenic viruses and bacteria, respectively. Increasing the Ca²⁺ concentration from 1 to 4.8 mM (along with background monovalent ions) resulted in complete attenuation (>6-log decrease in C/C₀) of MS-2, but caused only a 1-log reduction (C/C₀ = 0.1) in the concentration of the microspheres. Decreasing grain size from medium sand (d₅₀ = 0.70 mm) to fine sand (d₅₀ = 0.34 mm) resulted in substantial decreases in effluent concentrations of both the MS-2 (5-log decrease) and microspheres (>2.5-log decrease). Comparison of observed colloid retention to that predicted by a recently published correlation equation for colloid filtration revealed that the model can considerably underpredict (by 4 orders of magnitude or more) colloid retention by angular sand over distances as short as 20 cm. This indicates that state-of-the-art colloid filtration models are still limited in applicability to natural systems.     

Environmental occurrence, fate and transformation of benzodiazepines in water treatment

Benzodiazepine derivatives are prescribed in large quantities globally and are potentially new emerging environmental contaminants. Unfortunately, a dearth of data exists concerning occurrence, persistence and fate in the environment. This paper redresses this by reviewing existing literature, assessing the occurrence of selected benzodiazepine anxiolytics (diazepam, oxazepam and bromazepam) in wastewater influent and effluent and surface water from Slovenia, evaluating their removal during water treatment and identifying the transformation products formed during water treatment. Their occurrence was monitored in hospital effluent, river water and in wastewater treatment plant influent and effluent. The study reveals the presence of benzodiazepine derivatives in all samples with the highest amounts in hospital effluents: 111 ng L⁻¹, 158 ng L⁻¹ and 72 ng L⁻¹ for diazepam, bromazepam and oxazepam, respectively. Removal efficiencies with respect to biological treatment of diazepam were 16-18% (oxic), 18-32% (anoxic → oxic), 53-76% (oxic → anoxic) and 83% (oxic → anoxic → oxic → anoxic cascade bioreactors), while the removal oxazepam was 20-24% under anoxic conditions. Coupled biological and photochemical treatment followed by the adsorption to activated carbon resulted in a removal efficiency of 99.99%. Results reveal the recalcitrant nature of benzodiazepine derivatives and suggest that only combinational treatment is sufficient to remove them. In addition, eight novel diazepam and four novel oxazepam transformation products are reported.     

Adsorption of dissolved organic matter onto activated carbon--the influence of temperature, absorption wavelength, and molecular size

In this study, batch and column adsorption experiments with granular activated carbon (GAC) were carried out for removing dissolved organic matter (DOM) of a pond water at different water temperatures (5, 20, and 35 °C). The water was characterized before and after the adsorption step using UV/VIS spectroscopy and size-exclusion chromatography (SEC) combined with diode array detection (DAD). DOM breakthrough of GAC filters has been found to be slower at higher water temperatures, the DOM removal being most effective at 35 °C. UV/VIS spectra and SEC chromatograms of water samples treated at different water temperatures indicate that an increase in temperature especially supports the adsorption of small DOM molecules as well as molecules absorbing at higher wavelengths, specifying aromatic structures of DOM. SEC-DAD has been demonstrated to be an efficient method for characterizing DOM of natural waters and for detecting relative changes of DOM during the water treatment process.