Aerated treatment pond technology with biofilm promoting mats for the bioremediation of benzene, MTBE and ammonium contaminated groundwater

A novel aerated treatment pond for enhanced biodegradation of groundwater contaminants was tested under field conditions. Coconut fibre and polypropylene textiles were used to encourage the development of contaminant-degrading biofilms. Groundwater contaminants targeted for removal were benzene, methyl tert-butyl ether (MTBE) and ammonium. Here, we present data from the first 14 months of operation and compare contaminant removal rates, volatilization losses, and biofilm development in one pond equipped with coconut fibre to another pond with polypropylene textiles. Oxygen concentrations were constantly monitored and adjusted by automated aeration modules. A natural transition from anoxic to oxic zones was simulated to minimize the volatilization rate of volatile organic contaminants. Both ponds showed constant reductions in benzene concentrations from 20 mg/L at the inflow to about 1 μg/L at the outflow of the system. A dynamic air chamber (DAC) measurement revealed that only 1% of benzene loss was due to volatilization, and suggests that benzene loss was predominantly due to aerobic mineralization. MTBE concentration was reduced from around 4 mg/L at the inflow to 3.4-2.4 mg/L in the system effluent during the first 8 months of operation, and was further reduced to 1.2 mg/L during the subsequent 6 months of operation. Ammonium concentrations decreased only slightly from around 59 mg/L at the inflow to 56 mg/L in the outflow, indicating no significant nitrification during the first 14 months of continuous operation. Confocal laser scanning microscopy (CLSM) demonstrated that microorganisms rapidly colonized both the coconut fibre and polypropylene textiles. Microbial community structure analysis performed using denaturing gradient gel electrophoresis (DGGE) revealed little similarity between patterns from water and textile samples. Coconut textiles were shown to be more effective than polypropylene fibre textiles for promoting the recruitment and development of MTBE-degrading biofilms. Biofilms of both textiles contained high numbers of benzene metabolizing bacteria suggesting that these materials provide favourable growth conditions for benzene degrading microorganisms.     

Occurrence of seven artificial sweeteners in the aquatic environment and precipitation of Tianjin,China

Seventy water samples, including wastewaters, tap waters, fresh surface waters, coastal waters, groundwaters, and precipitation samples, from Tianjin, China, were analyzed for seven commonly used artificial sweeteners (ASs). The concentrations of the investigated ASs were generally in the order of wastewater treatment plant (WWTP) influent > WWTP effluent > surface water > tap water > groundwater ≈ precipitation, while the composition profiles of ASs varied in different waters. Acesulfame, sucralose, cyclamate, and saccharin were consistently detected in surface waters and ranged from 50 ng/L to 0.12 mg/L, while acesulfame was the dominant AS in surface and tap waters. Aspartame was found in all of the surface waters at a concentration up to 0.21 μg/L, but was not found in groundwaters and tap waters. Neotame and neohesperidin dihydrochalcone were less frequently detected and the concentrations were low. The concentrations of the ASs in some of the surface waters were of the same order with those in the WWTP influents, but not with the effluents, indicating there are probably untreated discharges into the surface waters. The ASs were detected in precipitation samples with high frequency, and acesulfame, saccharin, and cyclamate were the predominant ASs, with concentrations ranging from 3.5 ng/L to 1.3 μg/L. A gross estimation revealed that precipitation may act as a source for saccharin and cyclamate in the surface environment of Tianjin city. Moreover, the presence of ASs in the atmosphere was primarily assessed by taking 4 air samples to evaluate their potential source in precipitation.     

Comparison of chlorine and chloramine in the release of mercury from dental amalgam

The purpose of this project was to compare the ability of chlorine (HOCl/OCl⁻) and monochloramine (NH₂Cl) to mobilize mercury from dental amalgam. Two types of amalgam were used in this investigation: laboratory-prepared amalgam and samples obtained from dental-unit wastewater. For disinfectant exposure simulations, 0.5 g of either the laboratory-generated or clinically obtained amalgam waste was added to 250 mL amber bottles. The amalgam samples were agitated by end-over-end rotation at 30 rpm in the presence of 1 mg/L chlorine, 10 mg/L chlorine, 1 mg/L monochloramine, 10 mg/L monochloramine, or deionized water for intervals of 0 h, 2 h, 4 h, 8 h, and 24 h for the clinically obtained amalgam waste samples and 4 h and 24 h for the laboratory-prepared samples. Chlorine and monochloramine concentrations were measured with a spectrophotometer. Samples were filtered through a 0.45 µm membrane filter and analyzed for mercury with USEPA standard method 245.7. When the two sample types were combined, the mean mercury level in the 1 mg/L chlorine group was 0.020 mg/L (n = 25, SD = 0.008). The 10 mg/L chlorine group had a mean mercury concentration of 0.59 mg/L (n = 25, SD = 1.06). The 1 mg/L chloramine group had a mean mercury level of 0.023 mg/L (n = 25, SD = 0.010). The 10 mg/L chloramine group had a mean mercury level of 0.024 mg/L (n = 25, SD = 0.011). Independent samples t-tests showed that there was a significant difference between the natural log mercury measurements of 10 mg/L chlorine compared to those of 1 mg/L and 10 mg/L chloramine. Changing from chlorine to chloramine disinfection at water treatment plants would not be expected to produce substantial increases in dissolved mercury levels in dental-unit wastewater.     

Characterization of effluent water qualities from satellite membrane bioreactor facilities

Membrane bioreactors (MBRs) are often a preferred treatment technology for satellite water recycling facilities since they produce consistent effluent water quality with a small footprint and require little or no supervision. While the water quality produced from centralized MBRs has been widely reported, there is no study in the literature addressing the effluent quality from a broad range of satellite facilities. Thus, a study was conducted to characterize effluent water qualities produced by satellite MBRs with respect to organic, inorganic, physical and microbial parameters. Results from sampling 38 satellite MBR facilities across the U.S. demonstrated that 90% of these facilities produced nitrified (NH₄-N <0.4 mg/L-N) effluents that have low organic carbon (TOC <8.1 mg/L), turbidities of <0.7 NTU, total coliform bacterial concentrations <100 CFU/100 mL and indigenous MS-2 bacteriophage concentrations <21 PFU/100 mL. Multiple sampling events from selected satellite facilities demonstrated process capability to consistently produce effluent with low concentrations of ammonia, TOC and turbidity. UV-254 transmittance values varied substantially during multiple sampling events indicating a need for attention in designing downstream UV disinfection systems. Although enteroviruses, rotaviruses and hepatitis A viruses (HAV) were absent in all samples, adenoviruses were detected in effluents of all nine MBR facilities sampled. The presence of Giardia cysts in filtrate samples of two of nine MBR facilities sampled demonstrated the need for an appropriate disinfection process at these facilities.     

Interactions of nanosilver with Escherichia coli cells in planktonic and biofilm cultures

Biofilms are often more resistant to toxic chemicals such as heavy metals and antimicrobial agents than planktonic cells. Nanosilver has a broad range of applications with strong antimicrobial activity. However, biofilm susceptibility to nanosilver toxicity is not well understood. We studied the bacterial activity in planktonic or biofilm cultures after nanosilver exposure using oxygen quenching fluorescence-based microrespirometry. We also determined the aggregation behavior and the spatial distribution of nanosilver having red fluorescence in biofilms of Escherichia coli expressing green fluorescent protein. At the same bacterial concentrations (3 × 10⁸ CFU/mL), biofilms were about four times more resistant to nanosilver inhibition than planktonic cells. The minimum bactericidal concentrations (MBCs) of nanosilver (size from 15 to 21 nm), defined as the lowest concentration that kills at least 99.9% of a planktonic or biofilm bacterial population, were 38 and 10 mg/L Ag, respectively. For comparison, silver ions were more toxic to E. coli than nanosilver with MBCs of 2.4 and 1.2 mg/L Ag for planktonic and biofilm cultures, respectively. Nanosilver was aggregated in the presence of planktonic or biofilm-forming cells resulting in an increase of average particle size by a factor of 15 and 40, respectively. The nanosilver particles were able to penetrate to approximately 40 μm in a thick biofilm after 1-h exposure. These findings suggested that biofilm resistance to nanosilver could be at least partially due to nanoparticle aggregation and retarded silver ion/particle diffusion.     

Adsorption of perchlorate and other oxyanions onto magnetic permanently confined micelle arrays (Mag-PCMAs)

The removal of oxyanions found in drinking water sources -perchlorate, nitrate, phosphate, and sulfate- onto magnetic permanently confined micelle arrays (Mag-PCMAs) was studied. We determined the removal efficiency in both competitive and non-competitive environments, as many of these anions are present in these sources. Mag-PCMA removed over 98% of the aqueous perchlorate anions across a concentration range of 60-500 μg/L. Nitrate was absorbed 100% over a concentration range of 10-35 mg/L as nitrate. Removal of phosphate was 95.7% for 0.2-2.45 mg/L as phosphate. Sulfate was 100% absorbed across a concentration range of 5-20 mg/L and an average 75.7% for 5-50 mg/L. The sorption isotherms followed a Freundlich relationship with K_f values of 2.00, 2.05, 1.9, and 3.86 mg/g for nitrate, perchlorate, phosphate, and sulfate respectively. Perchlorate and nitrate did not compete significantly for binding on Mag-PCMAs, with almost equal sorption, greater than 90%, for both anions in elevated concentrations. This is a distinguishing feature from ion exchange resins or activated carbon with cationic surfactants, where these anions have been shown to compete for sorption sites. At the concentrations studied, phosphate and sulfate also do not exhibit significant competition. Desorption for reuse was successful at pH 10. This reusable magnetic sorbent can thus be used to rapidly remove target anions such as perchlorate from water in the presence or absence of other oxyanions.     

Free nitrous acid inhibition on the aerobic metabolism of poly-phosphate accumulating organisms

In full-scale wastewater treatment systems, phosphorus removal typically occurs together with nitrogen removal. Nitrite, an intermediate of both the nitrification and denitrification processes, can accumulate in the reactor. The inhibitory effect of nitrite/free nitrous acid (FNA) on the aerobic metabolism of poly-phosphate accumulating organisms (PAOs) is investigated. A culture highly enriched (90 ± 5%) in Candidatus “Accummulibacter phosphatis”, a well-known PAO, was used to perform a series of batch experiments at various nitrite and pH levels. FNA was found to inhibit all key aerobic metabolic processes performed by PAOs, namely PHA oxidation, phosphate uptake, glycogen replenishment and growth. The inhibitory effect on the anabolic processes (growth, phosphate uptake and glycogen production) was much stronger than that on the catabolic processes (PHA oxidation). 50% inhibition on all anabolic processes occurred at FNA concentrations of approximately 0.5 × 10^?3 mg HNO₂–N/L (equivalent to 2.0 mg NO₂^?–N/L at pH 7.0), while full inhibition occurred at FNA concentrations of approximately 6.0 × 10^?3 mg HNO₂–N. These concentrations could be found in full-scale wastewater treatment systems that achieve nitrogen removal via the nitrite pathway. In comparison, PHA oxidation remained at 40–50% of the highest rate at FNA concentrations in the range 2.0 × 10^?3–10.0 × 10^?3 mg HNO₂–N/L. Interestingly, PAOs were able to reduce nitrite under aerobic conditions (DO ≈ 3 mg/L), with the rate increasing substantially with the FNA concentration. The inhibition on phosphate uptake was found to be reversible.     

A nationwide survey of NDMA in raw and drinking water in Japan

A nationwide survey of N-nitrosodimethylamine (NDMA) in both raw and finished water samples from drinking water treatment plants (DWTPs) in Japan was conducted. NDMA was analyzed by solid-phase extraction (SPE) followed by ultra performance liquid chromatography (UPLC) coupled with tandem mass spectrometry (MS/MS). NDMA was detected in 15 of 31 raw water samples collected in the summer at concentrations up to 2.6 ng/L, and in 9 of 28 raw water samples collected in winter at concentrations up to 4.3 ng/L. The NDMA concentrations were higher in raw water samples collected from treatment plants with catchment areas that have high population densities. The NDMA concentrations were higher in river water samples collected from the east and west of Japan than in those collected from other areas. NDMA was detected in 10 of 31 finished samples collected in summer at reduced concentrations of up to 2.2 ng/L, while 5 of 28 finished samples collected in winter showed NDMA concentrations up to 10 ng/L. The highest NDMA levels were detected in finished water samples collected from the Yodo River basin DWTP, which uses ozonation. Furthermore, evaluation of the process water produced at six advanced water treatment plants was conducted. Influent from the Yodo River indicated that the NDMA concentration increased during ozonation to as high as 20 ng/L, and then decreased with subsequent biological activated carbon treatment. To our knowledge, this is the first nationwide evaluation of NDMA concentrations in water conducted in Japan to date.     

Evaluation of toxic and interactive toxic effects of three agrochemicals and copper using a battery of microbiotests

Three commonly used test organisms of different trophic levels (Vibrio fischeri, Pseudokirchneriella subcapitata and Daphnia magna) were exposed to selected agrochemicals (fosthiazate, metalaxyl-M, imidacloprid) and copper, in single doses or in binary mixtures. The toxicity of each single compound varied up to two orders of magnitude, depending on the test species examined. V. fischeri was the most sensitive test organism regarding fosthiazate and metalaxyl-M, indicating an IC₅₀ value of 0.20 mg/L (0.17-0.25 mg/L) and 0.88 mg/L (0.35-1.57 mg/L), respectively. Imidacloprid was the least toxic compound, indicating an EC₅₀ value on D. magna of 64.6 mg/L (43.3-122.5 mg/L) and an IC₅₀ value on V. fischeri of 226 mg/L (159-322 mg/L), while for imidacloprid at a concentration of 1000 mg/L the effect on P. subcapitata was lower than 50%. Copper was the most toxic compound towards all test organisms exhibiting the highest toxic effect on P. subcapitata, with an IC₅₀ value of 0.05 mg/L (0.003-0.008 mg/L). The toxic effects of the binary mixtures have been compared to the theoretically expected effect, resulting from a simple mathematical model based on the theory of probabilities. The independent action model was used in order to predict the theoretically expected effect. The interactive effects were mostly antagonistic or additive, while in few cases (interactive effects of metalaxyl-M and copper on V. fischeri) a synergistic mode of action was observed for some concentration combinations. Experiments showed that interactive effects of chemicals may vary depending on the test species used as well as on the chemicals and their respective concentrations. Although most of the concentrations of chemicals tested in this study are higher than the ones usually found in natural environment, the evaluation of their interactive toxic effects using a battery of bioassays may comprise a useful tool for the estimation of the environmental hazard of chemicals.     

Mercury accumulation and attenuation at a rapidly forming delta with a point source of mining waste

The Walker Creek intertidal delta of Tomales Bay, California is impacted by a former mercury mine within the watershed. Eleven short sediment cores (10 cm length) collected from the delta found monomethylmercury (MMHg) concentrations ranging from 0.3 to 11.4 ng/g (dry wt.), with lower concentrations occurring at the vegetated marsh and upstream channel locations. Algal mats common to the delta's sediment surface had MMHg concentrations ranging from 7.5 to 31.5 ng/g, and the top 1 cm of sediment directly under the mats had two times greater MMHg concentrations compared to adjacent locations without algal covering. Spatial trends in resident biota reflect enhanced MMHg uptake at the delta compared to other bay locations. Eighteen sediment cores, 1 to 2 m deep, collected from the 1.2 km² delta provide an estimate of a total mercury (Hg) inventory of 2500 ± 500 kg. Sediment Hg concentrations ranged from pre-mining background conditions of approximately 0.1 μg/g to a post-mining maximum of 5 μg/g. Sediment accumulation rates were determined from three sediment cores using measured differences of ¹³⁷Cs activity. We estimate a pre-mining Hg accumulation of less than 20 kg/yr, and a period of maximum Hg accumulation in the 1970s and 1980s with loading rates greater than 50 kg/yr, corresponding to the failure of a tailings dam at the mine site. At the time of sampling (2003) over 40 kg/yr of Hg was still accumulating at the delta, indicating limited recovery. We attribute observed spatial evolution of elevated Hg levels to ongoing inputs and sediment re-working, and estimate the inventory of the anthropogenic fraction of total Hg to be at least 1500 ± 300 kg. We suggest ongoing sediment inputs and methylation at the deltaic surface support enhanced mercury levels for resident biota and transfer to higher trophic levels throughout the Bay.     

Removal of bisphenol A and 17α-ethinyl estradiol from landfill leachate using single-walled carbon nanotubes

In this study, the adsorption of bisphenol A (BPA) and 17α-ethinyl estradiol (EE2) from landfill leachate onto single-walled carbon nanotubes (SWCNTs) was investigated. Different leachate solutions were prepared by altering the pH, ionic strength, and dissolved organic carbon (DOC) in the solutions to mimic the varying water conditions that occur in leachate during the various stages of waste decomposition. The youngest and oldest leachate solutions contained varying DOC and background chemistry and were represented by leachate Type A (pH = 5.0; DOC = 2500 mg/L; conductivity = 12,500 μS/cm; [Ca²⁺] = 1200 mg/L; [Mg²⁺] = 470 mg/L) and Type E (pH = 7.5; DOC = 250 mg/L; conductivity = 3250 μS/cm; [Ca²⁺] = 60 mg/L; [Mg²⁺] = 180 mg/L). These solutions were subsequently combined in different ratios to produce intermediate solutions, labeled B-D, to replicate time-dependent changes in leachate composition. Overall, a larger fraction of EE2 was removed as compared to BPA, consistent with its higher log K_OW value. The total removal of BPA and EE2 decreased in older leachate solutions, with the adsorptive capacity of SWCNTs decreasing in the order of leachate Type A > Type B > Type C > Type D > Type E. An increase in the pH from 3.5 to 11 decreased the adsorption of BPA by 22% in young leachate and by 10% in old leachate. The changes in pH did not affect the adsorption of EE2 in the young leachate, but did reduce adsorption by 32% in the old leachate. Adjusting the ionic strength using Na⁺ did not significantly impact adsorption, while increasing the concentration of Ca²⁺ resulted in a 12% increase in the adsorption of BPA and a 19% increase in the adsorption of EE2. DOC was revealed to be the most influential parameter in this study. In the presence of hydrophilic DOC, represented by glucose in this study, adsorption of the endocrine disrupting compounds (EDCs) onto the SWCNTs was not affected. In the absence of SWCNTs, hydrophobic DOC (i.e., humic acid) adsorbed 15-20% of BPA and EE2. However, when the humic acid and SWCNTs were both present, the overall adsorptive capacity of the SWCNTs was reduced. Hydrophobic (π-π electron donor-acceptor) interactions between the EDCs and the constituents in the leachate, as well as interactions between the SWCNTs and the EDCs, are proposed as potential adsorption mechanisms for BPA and EE2 onto SWCNTs.     

Inactivation of bacteriophage MS2 upon exposure to very low concentrations of chlorine dioxide

This study investigates the effects of very low concentrations of ClO₂ applied in drinking water practice on the inactivation of bacteriophage MS2. Concentrations of 0.5 mg/L, 0.1 mg/L and 0.02 mg/L ClO₂ inactivated at least 5 log units of MS2 after an exposure time of approximately 20, 50 and 300 min respectively. When the ClO₂ concentration was as low as 0.005 mg/L, inactivation of 1 log unit MS2 was observed after 300 min exposure. Increasing the contact time to 24 h did not increase the inactivation any further. Non-linear inactivation kinetics (tailing) were observed for all conditions tested. Repeated addition of MS2 to the reactor showed that tailing was not caused by a reduction of the biocidal effect of ClO₂ during disinfection. The Modified Chick-Watson, the Efficiency Factor Hom (EFH) model and the Modified Cerf model, a modification of the two-fraction Cerf model, were fitted to the non-linear inactivation curves. Both the EFH and the modified Cerf model did fit accurately to the inactivation data of all experiments. The good fit of the Modified Cerf model supports the hypothesis of the presence of two subpopulations. Our study showed that ClO₂ is an effective disinfectant against model organism MS2, also at the low concentrations applied in water treatment practice. The inactivation kinetics followed a biphasic pattern due to the presence of a more ClO₂-resistant subpopulation of MS2 phages, either caused by population heterogeneity or aggregation/adhesion of MS2.     

Microbial transformations of arsenic: mobilization from glauconitic sediments to water

In the Inner Coastal Plain of New Jersey, arsenic (As) is released from glauconitic sediment to carbon- and nutrient-rich shallow groundwater. This As-rich groundwater discharges to a major area stream. We hypothesize that microbes play an active role in the mobilization of As from glauconitic subsurface sediments into groundwater in the Inner Coastal Plain of New Jersey. We have examined the potential impact of microbial activity on the mobilization of arsenic from subsurface sediments into the groundwater at a site on Crosswicks Creek in southern New Jersey. The As contents of sediments 33-90 cm below the streambed were found to range from 15 to 26.4 mg/kg, with siderite forming at depth. Groundwater beneath the streambed contains As at concentrations up to 89 μg/L. Microcosms developed from site sediments released 23 μg/L of As, and active microbial reduction of As(V) was observed in microcosms developed from site groundwater. DNA extracted from site sediments was amplified with primers for the 16S rRNA gene and the arsenate respiratory reductase gene, arrA, and indicated the presence of a diverse anaerobic microbial community, as well as the presence of potential arsenic-reducing bacteria. In addition, high iron (Fe) concentrations in groundwater and the presence of iron-reducing microbial genera suggests that Fe reduction in minerals may provide an additional mechanism for release of associated As, while arsenic-reducing microorganisms may serve to enhance the mobility of As in groundwater at this site.     

Boron bioremoval by a newly isolated Chlorella sp. and its stimulation by growth stimulators

It has been well documented that excess concentrations of boron (B) causes toxic effects on many of the environmental systems. Although Chlorella sp. has been studied to remove pollutants from water, its capacity to remove B has not been investigated yet. Boron removal levels of newly isolated Chlorella sp. were investigated in BG 11 media with stimulators as triacontanol (TRIA) and/or sodium bicarbonate (NaHCO₃) and without them, to test if they could increase the removal efficiency by increasing biomass. The assays were performed to determine the effect of different medial compositions, B concentrations, pH and biomass concentrations onto removal efficiency. Boron removal was investigated at 5-10 mg/L range at pH 8 in different medial compositions and maximum removal yield was found as 32.95% at 5.45 mg/L B in media with TRIA and NaHCO₃. The effect of different pH values on the maximum removal yield was investigated at pH 5-9, and the optimum pH was found again 8. The interactive effect of biomass concentration and B removal yield was also investigated at 0.386-1.061 g wet weight/L biomass. The highest removal yield was found as 38.03% at the highest biomass range. This study highlights the importance of using new isolate Chlorella sp. as a new biomaterial for B removal process of waters containing B.     

Occurrence and formation potential of N-nitrosodimethylamine in ground water and river water in Tokyo

N-nitrosodimethylamine (NDMA), a disinfection byproduct of water and wastewater treatment processes, is a potent carcinogen. We investigated its occurrence and the potential for its formation by chlorination (NDMA-FP_2Cl) and by chloramination (NDMA-FP_2NHCl) in ground water and river water in Tokyo. To characterize NDMA precursors, we revealed their molecular weight distributions in ground water and river water. We collected 23 ground water and 18 river water samples and analyzed NDMA by liquid chromatography-tandem mass spectrometry. NDMA-FP_2Cl was evaluated by chlorinating water samples with free chlorine for 24 h at pH 7.0 while residual free chlorine was kept at 1.0-2.0 mgCl₂/L. NDMA-FP_2NHCl was evaluated by dosing water samples with monochloramine at 140 mgCl₂/L for 10 days at pH 6.8. NDMA precursors and dissolved organic carbon (DOC) were fractionated by filtration through 30-, 3-, and 0.5 kDa membranes. NDMA concentrations were <0.5-5.2 ng/L (median: 0.9 ng/L) in ground water and <0.5-3.4 ng/L (2.2 ng/L) in river water. NDMA concentrations in ground water were slightly lower than or comparable to those in river water. Concentrations of NDMA-FP_2Cl were not much higher than concentrations of NDMA except in samples containing high concentrations of NH₃ and NDMA precursors. The increased NDMA was possibly caused by reactions between NDMA precursors and monochloramine unintentionally formed by the reaction between free chlorine and NH₃ in the samples. NDMA precursors ranged from 4 to 84 ng-NDMA eq./L in ground water and from 11 to 185 ng-NDMA eq./L in river water. Those in ground water were significantly lower than those in river water, suggesting that NDMA precursors were biodegraded, adsorbed, or volatilized during infiltration. The molecular weight of NDMA precursors in river water was dominant in the <0.5 kDa fraction, followed by 0.5-3 kDa. However, their distribution was inconsistent in ground water: one was dominant in the <0.5 kDa fraction, and the other in 0.5-3 kDa. Molecular weight distributions of NDMA precursors were very different from those of DOC. This is the first study to reveal the widespread occurrence and characterization of NDMA precursors in ground water.     

Evaluation and modeling of benzalkonium chloride inhibition and biodegradation in activated sludge

The inhibitory effect and biodegradation of benzalkonium chloride (BAC), a mixture of alkyl benzyl dimethyl ammonium chlorides with different alkyl chain lengths, was investigated at a concentration range from 5 to 20 mg/L and different biomass concentrations in an activated sludge system. A solution containing glucose and mineral salts was used as the wastewater in all the assays performed. The inhibition of respiratory enzymes was identified as the mode of action of BAC as a result of oxygen uptake rate analysis performed at BAC concentrations ranging between 5 and 70 mg/L. The glucose degradation in the activated sludge at different BAC and biomass concentrations was well-described with Monod kinetics with competitive inhibition. The half-saturation inhibition constant (K_I) which is equivalent to EC₅₀ of BAC for the activated sludge tested ranged between 0.12 and 3.60 mg/L. The high K_I values were recorded at low BAC-to-biomass ratios, i.e. less than 10 mg BAC/g VSS, at which BAC was almost totally adsorbed to biomass and not bioavailable. BAC degradation started as soon as glucose was totally consumed. Although BAC was almost totally adsorbed on the biomass, it was degraded completely. Therefore, BAC degradation was modeled using two-phase biodegradation kinetics developed in this study. This model involves rapid partitioning of BAC to biomass and consecutive degradation in both aqueous and solid phases. The aqueous phase BAC degradation rate was twenty times, on average, higher than the solid phase degradation rate. The specific aqueous (k_I1) and solid (k_I2) phase BAC utilization rate constants were 1.25 and 0.31 mg BAC/g VSS h, respectively. The findings of this study would help to understand the reason of extensive distribution of quaternary ammonium compounds in wastewater treatment plant effluents and in natural water systems although QACs are biodegradable, and develop strategies to avoid their release and accumulation in the environment.     

Dynamics of Fe(II), sulphur and phosphate in pilot-scale constructed wetlands treating a sulphate-rich chlorinated hydrocarbon contaminated groundwater

Long-term investigations were carried out in two pilot-scale horizontal subsurface flow constructed wetlands (planted and unplanted) with an iron-rich soil matrix for treating sulphate-rich groundwater which was contaminated with low concentrations of chlorinated hydrocarbons. The temporal and spatial dynamics of pore-water sulphide, Fe(II) and phosphate concentrations in the wetland beds were characterized and the seasonal effects on sulphide production and nitrification inhibition were evaluated. The results demonstrated that the pore-water sulphide concentrations gradually increased from less than 0.2 mg/L in 2005 to annual average concentrations of 15 mg/L in 2010, while the pore-water Fe(II) concentrations decreased from 35.4 mg/L to 0.3 mg/L. From 2005 to 2010, the phosphate removal efficiency declined from 91% to 10% under a relatively constant inflow concentration of 5 mg/L. The pronounced effect of plants was accompanied by a higher sulphate reduction and ammonium oxidation in the planted bed, as compared to the unplanted control. A high tolerance of plants towards sulphide toxicity was observed, which might be due to the detoxification of sulphide by oxygen released by the roots. However, during the period of 2009-2010, the nitrification was negatively impacted by the sulphide production as the reduction in the removal of ammonium from 75% to 42% (with inflow concentration of 55 mg/L) correlated with the increasing mean annual sulphide concentrations. The effect of the detoxification of sulphide and the immobilization of phosphate by the application of the iron-rich soil matrix in the initial years was proven; however, the life-span of this effect should not only be taken into consideration in further design but also in scientific studies.     

Ambient trace element background concentrations in soils and their use in risk assessment

The definition of ambient background concentrations (ABCs) is used in this study to assess the potential environmental risk of trace elements in soils and parent materials from Granada, Spain. Two different layers of soil (0-20 and 20-40 cm) and parent material samples were collected at 93 sites. From cumulative frequency distribution curves, ABCs for As, Co, Cu, Cr, Ni, Pb and Zn were estimated at 3.5-20, 7-23, 13-25.6, 29-66, 7-20, 15-36, and 5.5-76 mg kg^− 1, respectively. Tukey box-plots were used to discriminate different concentration classes and identify potentially contaminated sites. Weakly-weathered soils (Entisols) over carbonate materials showed the lowest background contents, the most developed soils (Alfisols) over metamorphic rocks the highest ones. Outliers were mainly found near a former iron mine where arsenic concentrations were by far exceeding the corresponding regional ABC. These soils were however, not toxic to Escherichia coli and Vibrio fischeri. The prediction of site-specific ABCs together with bioavailability and toxicity assessment is a valuable tool for giving further insight into the risk of trace elements in soils.     

Implications of organic carbon in the deterioration of water quality in reclaimed water distribution systems

Changes in water quality in reclaimed water distribution systems are a major concern especially when considering the potential for growth of pathogenic microbes. A survey of 21 wastewater process configurations confirmed the high quality effluent produced using membrane bioreactor (MBR) technology, but suggests that other technologies can be operated to produce similar quality. Data from an intensive twelve-month sampling campaign in four reclaimed water utilities revealed the important trends for various organic carbon parameters including total organic carbon (TOC), biodegradable dissolved organic carbon (BDOC), and assimilable organic carbon (AOC). Of the four utilities, two were conventional wastewater treatment with open reservoir storage and two employed MBR technology with additional treatment including UV, ozone, and/or chlorine disinfection. Very high BDOC concentrations occurred in conventional systems, accounting for up to 50% of the TOC loading into the system. BDOC concentrations in two conventional plants averaged 1.4 and 6.3 mg/L and MBR plants averaged less than 0.6 mg/L BDOC. Although AOC showed wide variations, ranging from 100 to 2000 μg/L, the AOC concentrations in the conventional plants were typically 3-10 times higher than in the MBR systems. Pipe-loop studies designed to understand the impact of disinfection on the microbiology of reclaimed water in the distribution system revealed that chlorination will increase the level of biodegradable organic matter, thereby increasing the potential for microbial growth in the pipe network. This study concludes that biodegradable organic carbon is an important factor in the microbial quality and stability of reclaimed water and could impact the public health risk of reclaimed water at the point of use.     

Effect of cadmium, lead and arsenic on the oviposition, hatching and embryonic survival of Biomphalaria glabrata

Biomphalaria glabrata is a widespread freshwater gastropod mollusc. The easy aquaculture of these organisms allow its use as an accessible tool for contamination bioassays. B. glabrata showed marked metabolic responses when exposed to cadmium, lead and arsenic. Those responses could also affect the reproduction of the snails. Taking into account this hypothesis, B. glabrata were exposed for 96 h (acute laboratory bioassays) to different concentrations of cadmium (0.1, 0.05 and 0 mg/L), lead (0.5, 0.1, 0.05 and 0 mg/L) and arsenic (0.5, 0.1, 0.05 and 0 mg/L). Snails were removed from the aquaria while eggs were left in the same contaminant concentrations. The effect of the assayed toxicants on snail reproduction was registered as the alterations of the total number of laid eggs (TNLE), hatching time and embryonic survival.At 0.10 mg/L cadmium significantly decreased the TNLE (p < 0.05) and no embryos survived. The lowest assayed level (0.05 mg/L) of cadmium, delayed the hatching time twice when it was compared with the control group (p < 0.01).Lead decreased the TNLE at 0.5 mg/L level (p < 0.01). The other assayed doses (0.05 and 0.10 mg/L) also decreased embryonic survival significantly (p < 0.05 and p < 0.01 respectively) and extended twice the time to hatching (p < 0.01). The 0.50 mg/L level killed all embryos.Arsenic at all studied concentrations decreased the TNLE (p < 0.05) while the hatching time was increased by 50%. Embryo survival only decreased at the highest level (0.5 mg/L) of arsenic assayed.In summary, the acute exposure (96 h) to cadmium lead and arsenic, altered the reproduction of B. glabrata, modifying the TNLE, hatching time and embryonic survival.