Removal of pharmaceuticals and personal care products (PPCPs) from urban wastewater in a pilot vertical flow constructed wetland and a sand filter

Removal efficiencies and elimination kinetics of 13 pharmaceuticals and personal care products (PPCPs) and BOD5, TSS, and ammonium were evaluated in a pilot vertical subsurface-flow constructed wetland (VFCW) and compared with those obtained by a sand filter. On the basis of the observed removals, the PPCPs studied were grouped in relation to their removal efficiency into (i) PPCPs very efficiently removed, that is, >95% removal in one of the systems (caffeine, salicylic acid, methyl dihydrojasmonate, CA-ibuprofen, hydrocinnamic acid, oxybenzone, ibuprofen, OH-ibuprofen); (ii) PPCPs moderately removed, with removals between 70 and 90% in the two systems (naproxen, diclofenac, galaxolide, and tonalide); and finally (iii) PPCPs poorly removed, with elimination rates of <30% (carbamazepine). At design hydraulic loading rate (HLR) the planted VFCW and the nonplanted SF exhibited similar PPCP removal efficiencies, but the VFCWwas less sensitive to removal decline in overloading conditions (up to 2 times the design HLR). Moreover, under a clogging simulation, the HLR and the presence of vegetation were some of the key aspects affecting the PPCPs, BOD5, and ammonium removal from domestic wastewater. The VFCW evaluated was more efficient in terms of removal efficiency and loading rate for most of the PPCPs studied in comparison to constructed wetlands of other configurations (i.e., horizontal subsurface flow) and SF (nonplanted). The shorter hydraulic residence time (a few hours) in VFCW compared to that in other CW configurations ranging from days to weeks makes VFCWs a very appropriate wastewater treatment option in space-limited areas.     

Fate of endocrine-disruptor, pharmaceutical, and personal care product chemicals during simulated drinking water treatment processes

The potential occurrence of endocrine-disrupting compounds (EDCs) as well as pharmaceuticals and personal care products (PPCPs) in drinking water supplies raises concern over the removal of these compounds by common drinking water treatment processes. Three drinking water supplies were spiked with 10 to 250 ng/L of 62 different EDC/ PPCPs; one model water containing an NOM isolate was spiked with 49 different EDC/PPCPs. Compounds were detected by LC/MS/MS or GC/MS/MS. These test waters were subjected to bench-scale experimentation to simulate individual treatment processes in a water treatment plant (WTP). Aluminum sulfate and ferric chloride coagulants or chemical lime softening removed some polyaromatic hydrocarbons (PAHs) but removed <25% of most other EDC/ PPCPs. Addition of 5 mg/L of powder activated carbon (PAC) with a 4-h contact time removed 50% to >98% of GC/ MS/MS compounds (more volatile) and 10% to >95% of LC/ MS/MS compounds (more polar); higher PAC dosages improved EDC/PPCP removal. EDC/PPCP percentage removal was independent of the initial compound concentration. Octanol-water partition coefficients served as a reasonable indicator of compound removal under controlled PAC test conditions, except for EDC/PPCPs that were protonated or deprotonated at the test pH and some that contained heterocyclic or aromatic nitrogen. Separate chlorine or ozone experiments decreased the EDC/PPCP initial concentration by <10% to >90%; EDC/PPCPs were likely transformed to oxidation byproducts. Ozone oxidized steroids containing phenolic moieties (estradiol, ethynylestradiol, or estrone) more efficiently than those without aromatic or phenolic moieties (androstenedione, progesterone, and testosterone). EDC/PPCP reactivity with oxidants were separated into three general groups: (1) compounds easily oxidized (>80% reacted) by chlorine are always oxidized at least as efficiently by ozone; (2) 6 of the -60 compounds (TCEP, BHC, chlordane, dieldrin, heptachlor epoxide, musk ketone) were poorly oxidized (<20% reacted) by chlorine or ozone; (3) compounds (24 of 60) reacting preferentially (higher removals) with ozone rather than chlorine. Conventional treatment (coagulation plus chlorination) would have low removal of many EDC/PPCPs, while addition of PAC and/or ozone could substantially improve their removals. Existing strategies that predict relative removals of herbicides, pesticides, and other organic pollutants by activated carbon or oxidation can be directly applied for the removal of many EDC/PPCPs, but these strategies need to be modified to account for charged (protonated bases or deprotonated acids) and aliphatic species. Some compounds (e.g., DEET, ibuprofen, gemfibrozil) had low removals unless ozonation was used. Other compounds had low removals by all the WTP processes considered (atrazine, iopromide, meprobamate, TCEP), and removal processes capable of removing these types of compounds should be investigated.     

Behavior of selected pharmaceuticals in subsurface flow constructed wetlands: a pilot-scale study

Subsurface flow constructed wetlands (SSFs) constitute a wastewater treatment alternative to small communities due to the low operational cost, reduced energy consumption, and no sewage sludge production. Although much information is available about conventional water quality parameters in SSF constructed wetlands, few data are available regarding specific contaminants. In this paper, we focus on the behavior of three widely used pharmaceuticals (clofibric acid, ibuprofen, and carbamazepine) in two pilot SSF constructed wetlands planted with Phragmites australis and characterized by different water depths (i.e., 0.3 and 0.5 m). These SSFs partially treat the urban wastewater from a housing development (ca. 200 inhabitants). The three pharmaceuticals and bromide were continuously injected into the two SSFs during a period of 150-200 h, and the effluent concentration was simultaneously measured as 6 h composite samples. Their removal efficiency was calculated from the injected concentration, and the hydraulic parameters were evaluated and compared to bromide as tracer. In this regard, the behavior of clofibric acid was similar to that of bromide, and no sorption into the gravel bed occurred. On the other hand, carbamazepine showed a higher sorption than bromide and clofibric acid, which is attributable to its interaction on the gravel bed. Accordingly, the use of clofibric acid as a hydraulic tracer is proposed, taking into account its low residence time. Ibuprofen removal was 81% in the shallow SSF and 48% in the deep one. Differences in removal efficiency could be explained by the less anaerobic environment of the shallow wetland.     

Seasonal variation in the occurrence and removal of pharmaceuticals and personal care products in different biological wastewater treatment processes

The occurrence of 12 pharmaceuticals and personal care products (PPCPs) in two wastewater treatment plants in Beijing was studied monthly over the course of one year. The removal of PPCPs by three biological treatment processes including conventional activated sludge (CAS), biological nutrient removal (BNR), and membrane bioreactor (MBR) was compared during different seasons. Seasonal variations of PPCPs in the wastewater influent were discrepant, while in the wastewater effluent, most PPCPs had lower concentrations in the summer than in the winter. For the easily biodegradable PPCPs, the performance of MBR was demonstrated to be more stable than CAS or BNR especially during winter months. Diclofenac, trimethoprim, metoprolol, and gemfibrozil could be moderately removed by MBR, while their removal by CAS and BNR was much lower or even negligible. Nevertheless, no removal was achieved regardless of the season or the treatment processes for the recalcitrant PPCPs. Studies on the contribution of each tank of the MBR process to the total removal of four biodegradable PPCPs indicated the oxic tank was the most important unit, whereas membrane filtration made a negligible contribution to their elimination.     

Performance evaluation using a three compartment mass balance for the removal of volatile organic compounds in pilot scale constructed wetlands

To perform a general assessment of treatment efficiency, a mass balance study was undertaken for two types of constructed wetlands (CWs), planted gravel filters and plant root mat systems, for treating VOC (benzene; MTBE) polluted groundwater under field conditions. Contaminant fate was investigated in the respective water, plant, and atmosphere compartments by determining water and atmospheric contaminant loads and calculating contaminant plant uptake, thereby allowing for an extended efficiency assessment of CWs. Highest total VOC removal was achieved during summer, being pronounced for benzene compared to MTBE. According to the experimental results and the calculations generated by the balancing model, degradation in the rhizosphere and plant uptake accounted for the main benzene removal processes, of 76% and 13% for the gravel bed CW and 83% and 11% for the root mat system. Volatilization flux of benzene and MTBE was low (<5%) for the gravel bed CW, while in the root mat system direct contact of aqueous and gaseous phases favored total MTBE volatilization (24%). With this applied approach, we present detailed contaminant mass balances that allow for conclusive quantitative estimation of contaminant elimination and distribution processes (e.g., total, surface, and phytovolatilization, plant uptake, rhizodegradation) in CWs under field conditions.     

水中9种医药品与个人护理品污染物的电子束辐照降解分析

应用液相色谱串联四级杆质谱联用技术建立了水中5种抗生素类医药品与个人护理品（PPCPs）污染物、2种激素类PPCPs和2种受体拮抗剂类PPCPs的定性定量检测方法。应用电子辐照加速器初步探索了水中不同质量浓度PPCPs的降解研究,通过多个辐照剂量点的含量结果分析了初始质量浓度为5 ng/mL和100 ng/mL的磺胺甲噁唑、丙酸睾酮和西咪替丁的辐照降解规律,对初始质量浓度为100 ng/mL的9种PPCPs研究了辐照吸收剂量对降解率的影响。结果表明,PPCP质量浓度对辐照降解率无明显影响,同类型的不同PPCPs污染物降解规律和阈值明显不同,5种抗生素类PPCPs的降解速度为红霉素＜磺胺甲噁唑＜氯唑西林＜氧氟沙星＜利福昔明,辐照降解阈值分别是20.0 kGy、8.0 kGy、8.0 kGy、3.5 kGy、1.6 kGy,与降解速度基本呈现正比关系。     

Seasonal variations in concentrations of pharmaceuticals and personal care products in drinking water and reclaimed wastewater in southern California

Southern California imports nearly all of its potable water from two sources: the Colorado River and the California State Water Project (Sacramento-San Joaquin River Basin). Sewage treatment plant effluent (STPE) heavily impacts both of these sources. A survey of raw and treated drinking water from four water filtration plants in San Diego County showed the occurrence of several polar organic "pharmaceuticals and personal care products" (PPCP). These included phthalate esters, sunscreens, clofibrate, clofribric acid, ibuprofen, triclosan, and DEET. Several of these were also found in the finished water, such as di(ethylhexyl) phthalate, benzophenone, ibuprofen, and triclosan. Occurrence and concentrations of these compounds were highly seasonally dependent, and reached maximums when the flow of the San Joaquin River was low and the quantity of imported water was high. The maximum concentrations of the PPCPs measured in the raw water were correlated with low flow conditions in the Sacramento-San Joaquin Delta that feeds the State Water Project. The PPCP concentrations in raw imported water in the summer months approached that of reclaimed nonpotable wastewater.     

Factors affecting linear alkylbenzene sulfonates removal in subsurface flow constructed wetlands

The behavior of linear alkylbenzene sulfonate (LAS) and sulfophenyl carboxylate (SPC) biointermediates in a pilot subsurface flow constructed wetland (SFCW) is reported for the first time. The effects of wetland configuration and operation on their treatment efficiency were investigated. The pilot SFCW constituted by eight beds of 55 m2 with different aspect ratios (1 x 1; 1.5 x 1; 2 x 1; 2.5 x 1), two water depths (i.e., 0.47 and 0.27 cm) at 5 cm below surface and two medium sizes (i.e., D60 = 10 mm and 3.5 mm) planted with Phragmites sp. That SFCW pilottreats urban wastewater (i.e., 200 inhabitants) and was operated at four hydraulic loading rates (HLRs) (20, 27, 36, and 45 mm d(-1)). Influent and effluent sampling was carried out from May 2001 to January 2002 with a weekly pattern. Main results were as follows: (i) water depth has a major influence on the performance of SFCW for the LAS removal, and HLR shows significant effect on SPC evolution; (ii) water temperature has a significant effect on the LAS evolution; (iii) biodegradation of LAS and SPC can occur under sulfate-reducing environment and mixed conditions (i.e., sulfate-reducing and denitrification), but aerobic respiration cannot be excluded; and (iv) C13 LAS homologues were generally removed in higher extent than the shorter alkyl chain counterparts. In the most appropriate conditions, LAS and SPC can be biodegraded up to 71% and 11%, respectively, in the pilot SFCW evaluated.     

Preparation and evaluation of GAC-based iron-containing adsorbents for arsenic removal

Granular activated carbon-based, iron-containing adsorbents (As-GAC) were developed for effective removal of arsenic from drinking water. Granular activated carbon (GAC) was used primarily as a supporting medium for ferric iron that was impregnated by ferrous chloride (FeCl2) treatment, followed by chemical oxidation. Sodium hypochlorite (NaClO) was the most effective oxidant, and carbons produced from steam activation of lignite were most suitable for iron impregnation and arsenic removal. Two As-GAC materials prepared by FeCl2 treatment (0.025 -0.40 M) of Dacro 20 x 50 and Dacro 20 x 40LI resulted in a maximum impregnated iron of 7.89% for Dacro 20 x 50 and 7.65% for Dacro 20 x 40Ll. Nitrogen adsorption-desorption analyses showed the BET specific surface area, total pore volume, porosity, and average mesoporous diameter all decreased with iron impregnation, indicating that some micropores were blocked. SEM studies with associated EDS indicated that the distribution of iron in the adsorbents was mainly on the edge of As-GAC in the low iron content (approximately 1% Fe) sample but extended to the center at the higher iron content (approximately 6% Fe). When the iron content was > approximately 7%, an iron ring formed at the edge of the GAC particles. No difference in X-ray diffraction patterns was observed between untreated GAC and the one with 4.12% iron, suggesting that the impregnated iron was predominantly in amorphous form. As-GAC could remove arsenic most efficiently when the iron content was approximately 6%; further increases of iron decreased arsenic adsorption. The removal of arsenate occurred in a wide range of pH as examined from 4.4 to 11, but efficiency was decreased when pH was higher than 9.0. The presence of phosphate and silicate could significantly decrease arsenate removal at pH > 8.5, while the effects of sulfate, chloride, and fluoride were minimal. Column studies showed that both As(V) and As(III) could be removed to below 10 microg/L within 6000 empty bed volume when the groundwater containing approximately 50 microg/L of arsenic was treated.     

Arsenic removal from groundwater by household sand filters: comparative field study, model calculations, and health benefits

Arsenic removal efficiencies of 43 household sand filters were studied in rural areas of the Red River Delta in Vietnam. Simultaneously, raw groundwater from the same households and additional 31 tubewells was sampled to investigate arsenic coprecipitation with hydrous ferric iron from solution, i.e., without contact to sand surfaces. From the groundwaters containing 10-382 microg/L As, < 0.1-48 mg/L Fe, < 0.01-3.7 mg/L P, and 0.05-3.3 mg/L Mn, similar average removal rates of 80% and 76% were found for the sand filter and coprecipitation experiments, respectively. The filtering process requires only a few minutes. Removal efficiencies of Fe, phosphate, and Mn were > 99%, 90%, and 71%, respectively. The concentration of dissolved iron in groundwater was the decisive factor for the removal of arsenic. Residual arsenic levels below 50 microg/L were achieved by 90% of the studied sand filters, and 40% were even below 10 microg/L. Fe/As ratios of > or = 50 or > or = 250 were required to ensure arsenic removal to levels below 50 or 10 microg/L, respectively. Phosphate concentrations > 2.5 mg P/L slightly hampered the sand filter and coprecipitation efficiencies. Interestingly, the overall arsenic elimination was higher than predicted from model calculations based on sorption constants determined from coprecipitation experiments with artificial groundwater. This observation is assumed to result from As(lll) oxidation involving Mn, microorganisms, and possibly dissolved organic matter present in the natural groundwaters. Clear evidence of lowered arsenic burden for people consuming sand-filtered water is demonstrated from hair analyses. The investigated sand filters proved to operate fast and robust for a broad range of groundwater composition and are thus also a viable option for mitigation in other arsenic affected regions. An estimation conducted for Bangladesh indicates that a median residual level of 25 microg/L arsenic could be reached in 84% of the polluted groundwater. The easily observable removal of iron from the pumped water makes the effect of a sand filter immediately recognizable even to people who are not aware of the arsenic problem.     

Nitrogen removal in a small constructed wetland: an isotope mass balance approach

The nitrogen (N) removal potential of constructed wetlands is increasingly used to lower the N load from agricultural nonpoint sources to inland and coastal waters. To determine the removal efficiency and key factors limiting wetland N removal, N fluxes were studied in a small constructed wetland in Central Switzerland. With an isotope mass balance approach integrating the natural isotope signature of nitrate (NO3-, ammonium (NH4+), and particulate nitrogen (PN), the N transformations such as assimilation, mineralization, nitrification, and denitrification were quantified. On average, the wetland removed 45 g m(-2) yr(-1) N during the studied 2.5 years, corresponding to a removal efficiency of 27%. Denitrification contributed 94% to the N removal, while only 6% of the removed N accumulated in the sediments. Denitrification was most efficient during periods with an oxic water column overlying anoxic sediments, as NH4+ released during mineralization of sediment organic matter was completely nitrified and subsequently denitrified at the sediment-water interface. During water column anoxia, NH4+ accumulated in the water and fueled assimilation by duckweed and internal recycling. The NO3-N isotope signature in the wetland mainly reflected the mineralization of sediment organic matter and subsequent nitrification, while denitrification at the sediment-water interface produced no fractionation.     

Application of pulsed corona induced plasma chemical process to an industrial incinerator

Pulsed corona induced plasma chemical process (PPCP) has been investigated for the simultaneous removal of NO(x) (nitrogen oxides) and SO2 (sulfur dioxide) from the flue gas emission. It is one of the world's largest scales of PPCP for treating NO(x) and SO2 simultaneously. A PPCP unit equipped with an average 120 kW modulator has been installed and tested at an industrial incinerator with the gas flow rate of 42 000 m3/h. To improve the removal efficiency of SO2 and NO(x), ammonia (NH3) and propylene (C3H6) were used as chemical additives. It was observed that the pulsed corona induced plasma chemical process made significant NO(x) and SO2 conversion with reasonable electric power consumption. The ammonia injection was very effective in the enhancement of SO2 removal. NO removal efficiency was significantly improved by injecting a C3H6 additive. In the experiments, the removal efficiencies of SO2 and NO(x) were approximately 99 and 70%, respectively. The specific energy consumption during the normal operation was approximately 1.4 Wh/m3, and the nanopulse conversion efficiency of 64.3% was achieved with the pulsed corona induced plasma chemical process.     

Prebiotic potential of a refined product containing pectic oligosaccharides

Apple pomace samples were subjected to Simultaneous Saccharification and Fermentation (SSF) to yield a medium containing mainly lactic acid and oligosaccharides. After lactic acid removal by ion exchange, the SSF medium was refined by a two-step (diafiltration-concentration) membrane treatment. Limited losses of glucooligosaccharides, galactooligosaccharides, xylooligosaccharides and arabinooligosaccharides were noticed in permeates, whereas the concentrate from the second stage showed low concentrations of lactic acid, arabinose and NaCl, which were extensively removed in the refining process. About 60% other the non-saccharide compounds present in the solution fed to membranes were removed in permeates, whereas oligogalacturonides were quantitatively recovered in the final concentrate. The refined product was assayed for its prebiotic potential by means of in vitro fermentability assays performed with individual microbial strains or human fecal inocula. In this latter case, the dynamics of microbial populations was assessed by Fluorescent In Situ Hybridization (FISH). The experimental results proved the prebiotic effects caused by the refined product obtained in this work, which included the promotion of beneficial bacterial growth and the increase of short chain fatty acids (SCFA) concentrations.     

Occurrence and fate of carbamazepine,clofibric acid,diclofenac, ibuprofen,ketoprofen, and naproxen in surface waters

Although various single-concentration measurements of pharmaceuticals are available in the literature, detailed information on the variation over time of the concentration and the load in wastewater effluents and rivers and on the fate of these compounds in the aquatic environment are lacking. We measured the concentrations of six pharmaceuticals, carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen, in the effluents of three wastewater treatment plants (WWTPs), in two rivers and in the water column of Lake Greifensee (Switzerland) over a time period of three months. In WWTP effluents, the concentrations reached 0.95 microg/L for carbamazepine, 0.06 microg/L for clofibric acid, 0.99 microg/L for diclofenac, 1.3 microg/L for ibuprofen, 0.18 microg/L for ketoprofen, and 2.6 microg/L for naproxen. The relative importance in terms of loads was carbamazepine, followed by diclofenac, naproxen, ibuprofen, clofibric acid, and ketoprofen. An overall removal rate of all these pharmaceuticals was estimated in surface waters, under real-world conditions (in a lake), using field measurements and modeling. Carbamazepine and clofibric acid were fairly persistent. Phototransformation was identified as the main elimination process of diclofenac in the lake water during the study period. With a relatively high sorption coefficient to particles, ibuprofen might be eliminated by sedimentation. For ketoprofen and naproxen, biodegradation and phototransformation might be elimination processes. For the first time, quantitative data regarding removal rates were determined in surface waters under real-world conditions. All these findings are important data for a risk assessment of these compounds in surface waters.     

Removal of bacteria from coastal seawater by foam separation using dispersed bubbles and surface-active substances

The removal of bacteria from rearing water and washing water in aquaculture systems, aquariums and fishing port facilities is the most important means of diminishing the risk of fish diseases, improving public health and ensuring high food quality. However, there are few methods of bacterial elimination, e.g., disinfection. Thus, it is necessary to develop a technology for bacterial removal from coastal seawater. In this study, the removal efficiency for several groups of bacteria by foam separation using dispersed bubbles and surface-active substances was determined using both batch equipment and a continuous-flow unit. By batch processing with only 1 mg/l milk casein added as a surface-active substance and by supplying bubbles, viable bacteria, enterococci, Vibrio, and Salmonella-like bacteria were removed effectively at removal efficiencies of 80% or greater. In addition, suspended solids were also removed from coastal seawater. However, fecal coliforms were difficult to remove by foam separation. The removal efficiency for viable bacteria was greater than 70% using a continuous system. Bacteria were concentrated in a very small amount of generated foam and removed from the water. The foam separation using dispersed bubbles and surface-active substances is a feasible convenient technology for seawater purification as a treatment prior to membrane filtration or ultraviolet irradiation.     

Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations

Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.     

Evaluation of pharmaceuticals and personal care products as water-soluble molecular markers of sewage

We examined the utility of 13 pharmaceuticals and personal care products (PPCPs) as molecular markers of sewage contamination in riverine, groundwater, and coastal environments. The PPCPs were crotamiton, ibuprofen, naproxen, ketoprofen, fenoprofen, mefenamic acid, thymol, triclosan, propyphenazone, carbamazepine, diethyltoluamide, ethenzamide, and caffeine. Measurements in 37 Japanese rivers showed positive correlations of riverine flux of crotamiton (r2 = 0.85), carbamazepine (r2 = 0.84), ibuprofen (r2 = 0.73), and mefenamic acid (r2 = 0.67) with the population in the catchments. In three surveys in the Tamagawa estuary, crotamiton, carbamazepine, and mefenamic acid behaved conservatively across seasons within a salinity range of 0.4-29 per thousand, suggesting their utility as molecular markers in coastal environments. Removal of ketoprofen and naproxen in the estuary was ascribed to photodegradation. Ibuprofen and thymol were removed from estuarine waters in summer by microbial degradation. Triclosan was removed by a combination of microbial degradation, photodegradation, and adsorption. These results were consistent with those of river water incubated for 8 d at 25 degrees C in the dark in order to examine the effects of biodegradation and photodegradation. Crotamiton was detected in groundwater from the Tokyo metropolitan area (12 out of 14 samples), suggesting wastewater leakage from decrepit sewers. Carbamazepine, ketoprofen, and ibuprofen (5/14), caffeine (4/14), and diethyltoluamide (3/14) were also detected in the groundwater, whereas the other carboxylic and phenolic PPCPs were not detected and were thought to be removed during their passage through soil. All the data demonstrated the utility of crotamiton and carbamazepine as conservative markers in freshwater and coastal environments. We recommend combining these conservative markers with labile PPCPs to detect inputs of poorly treated sewage.     

Organic/inorganic hybrid filters based on dendritic and cyclodextrin "nanosponges" for the removal of organic pollutants from water

Long-alkyl chain functionalized poly(propylene imine) dendrimer, poly(ethylene imine) hyperbranched polymer, and beta-cyclodextrin derivatives, which are completely insoluble in water, have the property of encapsulating organic pollutants from water. Ceramic porous filters can be impregnated with these compounds resulting in hybrid organic/ inorganic filter modules. These hybrid filter modules were tested for the effective purification of water, by continuous filtration experiments, employing a variety of water pollutants. It has been established that polycyclic aromatic hydrocarbons (PAHs) can be removed very efficiently (more than 95%), and final concentrations of several ppb (microg/ L) are easily obtained. Representatives of the pollutant group of trihalogen methanes (THMs), monoaromatic hydrocarbons (BTX), and pesticides (simazine) can also be removed (>80%), although the filters are saturated considerably faster in these cases.     

Perchlorate reduction by autotrophic bacteria attached to zerovalent iron in a flow-through reactor

Biological reduction of perchlorate by autotrophic microorganisms attached to zerovalent iron (ZVI) was studied in flow-through columns. The effects of pH, flow rate, and influent perchlorate and nitrate concentrations on perchlorate reduction were investigated. Excellent perchlorate removal performance (> or = 99%) was achieved at empty bed residence times (EBRTs) ranging from 0.3 to 63 h and an influent perchlorate concentration of 40-600 microg L(-1). At the longest liquid residence times, when the influent pH was above 7.5, a significant increase of the effluent pH was observed (pH > 10.0), which led to a decrease of perchlorate removal. Experiments at short residence times revealed that the ZVI column inoculated with local soil (Colton, CA) containing a mixed culture of denitrifiers exhibited much better performance than the columns inoculated with Dechloromonas sp. HZ for reduction of both perchlorate and nitrate. As the flow rate was varied between 2 and 50 mL min(-1), corresponding to empty bed contact times of 0.15-3.8 h, a maximum perchlorate elimination capacity of 3.0 +/- 0.7 g m(-3) h(-1) was obtained in a soil-inoculated column. At an EBRT of 0.3 h and an influent perchlorate concentration of 30 microg L(-1), breakthrough (> 6 ppb) of perchlorate in the effluent did not occur until the nitrate concentration in the influent was 1500 times (molar) greater than that of perchlorate. The mass of microorganisms attached on the solid ZVI/sand was found to be 3 orders of magnitude greater than that in the pore liquid, indicating that perchlorate was primarily reduced by bacteria attached to ZVI. Overall, the process appears to be a promising alternative for perchlorate remediation.     

Efficient visible light driven photocatalytic removal of RhB and NO with low temperature synthesized In(OH)xSy hollow nanocubes: a comparative study

In this work, we report that RhB and NO could be effectively removed under visible light with hollow In(OH)xSy nanocubes fabricated at a low temperature of 80 °C. The photocatalytic experiments revealed that these low temperature synthesized hollow In(OH)xSy nanocubes were more efficient than P25 and In(OH)xSy counterpart hydrothermally synthesized at 180 °C (In(OH)xSy-180). The porous structures, larger surface area, and new valence band of low temperature synthesized hollow In(OH)xSy nanocubes were thought to account for their superior photocatalytic activity. Among all the In(OH)xSy samples, the one with original S/In ratio of 0.500 in synthetic solution exhibited the highest photocatalytic removal efficiencies of RhB, while the other with original S/In ratio of 1.000 removed NO most efficiently. We systematically studied the photocatalytic process of RhB on In(OH)xSy and analyzed their different photocatalytic performances on removing RhB and NO. This study reveals that these hollow In(OH)xSy nanocubes are promising for environmental remediation.