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

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

A kinetic model for bioconcentration of lipophilic compounds by oligochaetes

Bioconcentration of lipophilic compounds by oligochaete worms has been modelled as consecutive partition equilibria, firstly between sediment and interstitial water and then between interstitial water and worm. Each interphase process has been assumed to proceed according to first order kinetics. The resulting expression for the biotic concentration as a function of time has been fitted to experimental data over the range 3 ≤ log K_ow ≤ 6 by varying the kinetic rate constants using a constrained, nonlinear least squares procedure. Relationships between uptake and clearance rate constants and log K_ow are in accord with existing theory. The regression equation between the equilibrium bioconcentration factor, K_B, and K_ow also is in general agreement with previous relationships established for other aquatic organisms. For many of the high K_owcompounds equilibration times are longer than can be reasonably achieved in laboratory experiments. The methodology presented has an advantage in that it does not require the establishment of equilibrium for the estimation of K_B, since the ratio of derived rate constants rather than biotic and water concentrations has been used.     

Comparative chronic toxicity of homo- and heterocyclic aromatic compounds to benthic and terrestrial invertebrates: Generalizations and exceptions

The aim of the present study was to elucidate consistent patterns in chronic polycyclic aromatic compound (PAC) toxicity to soil and sediment inhabiting invertebrates. Therefore we examined our experimental dataset, consisting of twenty-one chronic effect concentrations for two soil invertebrates (Folsomia candida and Enchytraeus cripticus) and two sediment invertebrates (Lumbriculus variegatus and Chironomus riparius) exposed to six PACs (two homocyclic isomers, anthracene and phenanthrene; two azaarene isomers: acridine and phenanthridine; and two azaarene transformation products, acridone and phenanthridone). In order to determine if effect concentrations were accurately predicted by existing toxicity-K_ow relationships describing narcosis, chronic pore water effect concentrations were plotted jointly against logK_ow. Fifteen of the twenty-one effect concentrations (71%) were above the lower limit for narcosis, showing that narcosis was the main mode of action for the majority of the tested homo- and heterocyclic PACs during chronic exposure. Toxicity of all tested compounds to soil organisms was accurately described by the toxicity-K_ow relationship. However, for the sediment invertebrates exposed to some of the tested heterocyclic PACs deviations from narcosis were identified, related to specific physicochemical properties of the test compounds and/or species specific sensitivities. It is concluded that existing toxicity-K_ow relationships describing narcosis in some cases underestimate chronic PAC toxicity to sediment inhabiting invertebrates.     

Bioconcentration and metabolism of phenyltin chlorides in carp

Bioconcentration factors (BCF) in carp (Cyprinus carpio L.) and partition coefficients between n-octanol and water (P_ow) were measured for triphenyltin chloride (Ph₃SnCl), diphenyltin dichtende (Ph₂SnCl₂) and monophenyltin trichloride (PhSnCl₃). Log P_ow was 2.11 for Ph₃SnCl, 1.43 for Ph₂SnCl₂ and 1.73 for PhSnCl₃. The order of log BCF was kidney > liver > muscle gallbladder for Ph₃SnCl, liver > kidney > gallbladder > muscle for Ph₂SnCl₂ and kidney liver > gallbladder > muscle for PhSnCl₃. Further, metabolism in carp was studied on Ph₃SnCl. Ph₂Sn²⁺ and PhSn³⁺, the metabolites of Ph₃SnCl were detected in muscle and viscera. The ratio of Ph₃SnCl, Ph₂Sn²⁺ (Ph₂SnCl₂) and PhSn³⁺ (PhSnCl₃) concentrations by metabolism in each part of carp corresponded to that of BCF by carp for the same phenyltin chlorides.     

Prediction of the optimum pH for ammonia-n oxidation by nitrosomonas Europaea in well-aerated natural and domestic-waste waters

Three assumptions were needed to model whole-cell and cell-extract data showing how pH affects the rate and optimum pH of the first step of nitrification: (1) un-ionized ammonia-N is the substrate; (2) substrate ionization occurs; and (3) ampholytic ionization of only the rate-limiting enzyme-substrate complex, and not the free enzyme, controls the rate of ammonia-N oxidation. The rate was shown to obey a Michaelis-Menten rate law where the apparent maximum-velocity coefficient and the apparent half-saturation coefficient with V_m and K_m being the Michaelis-Menten maximum-velocity and half-saturation coefficients, respectively; K₁ and K₂, the acid dissociation coefficients for the enzyme; K₃, the acid dissociation coefficient for aqueous ammonium. The optimum pH (pH₀) was shown to decrease almost linearly with the logarithm of total ammonia-N concentration over the concentration range found in natural and domestic-waste waters: for N < ppm total ammonia-N.     

Separation,identification and quantification of components of industrial effluents with bioconcentration potential

A procedure for the separation, identification and quantification of components of industrial effluents that have the potential for bioconcentration has been developed and evaluated. Effluents were first extracted with a mixture of hexane and t-butyl methyl ether, and then fractionated into groups having log K_ow < 3, log K_ow from 3 to 5, and log K_ow > 5 by HPLC using a semi-preparative C₁₈ column and gradient elution with methanol/phosphate buffer. The fractions, having K_ow > 3, were derivatized, and after cleanup by open-column chromatography on silica gel, subjected to GC-MS analysis for identification. Compounds that were identified were quantified by GC using FID. The method has been validated using a spiked sample and an effluent, and evaluated by application to three widely different types of industrial effluents.     

Bioavailability of organic pollutants in boreal waters with varying levels of dissolved organic material

Dissolved organic matter (DOM) in 20 surface waters in Eastern Finland were characterized to examine relationships between structural and compositional properties of DOM and partition coefficients (K_p) describing sorption of four model contaminants to DOM and the bioavailability of contaminants by Daphnia magna. The hydrophobic acids (HbA), hydrophobic neutrals (HbN) and hydrophilic (HI) fractions of DOM were separated by XAD-8 resin. The K_Ps were measured by equilibrium dialysis. Model contaminants were benzo(a)pyrene (BaP), naphthalene (NAPH), 3.3′,4.4′-tetrachlorobiphenyl (TCB) and dehydroabietic acid (DHAA).DOM concentrations varied from 2.0 to 38.3 mg org. C/l in the water series. The percentage of HbA and the aromaticity of DOM, as indicated by the absorptivity at 270 nm (A₂₇₀) and hydrogen/carbon ratio (H/C ratio), increased with increasing DOM concentration. Significant correlations were observed between K_P of BAP, A₂₇₀ and HbA content of the DOM from different sources. For the other contaminants similar kinds of relationships between K_ps and quality parameters of DOM could not be found.The bioavailability of model compounds was decreased by increasing DOM concentration in the water series. For all four model contaminants, measured bioconcentration factors (BCF) correlated well with the A₂₇₀ of a water and HbA content of the DOM. These results show that the total DOM concentration is an important factor controlling the bioavailability of xenobiotics in natural waters. Besides the quantity also the quality of DOM, like proportion of HbA, can contribute in bioavailability.     

Plant crown traits and carbon sequestration capability by Platanus hybrida Brot. in Rome

Measurements of carbon dioxide (CO₂) concentration carried out in the city of Rome in the period January–December 2005 showed a mean yearly CO₂ concentration of 414 ± 45 ppm; polluted sites (P sites) had 21% higher CO₂ concentration than control sites (C sites). The significant (p < 0.01) correlation analysis between CO₂ concentration and traffic density measured during the study period at P sites showed that traffic density explained 51% of the CO₂ variation. The CO₂ trend during the traffic limitation days (provision imposed by ordinance of the City Council) did not show significant differences as regards regular traffic days, suggesting the ineffectiveness of this provision. Leaf area index (LAI) of Platanus hybrida Brot. was on an average 11% lower at P sites than at C ones associated with a lower total photosynthetic leaf surface area (SPT, 34% lower at P sites than at C ones). P. hybrida had a total carbon sequestration of 117 ± 13 kg year⁻¹ (mean value of P and C sites) playing an important role in sequestering CO₂. Thus, the choice of plant species for urban areas may be set out taking into account their own air amelioration capability. Plant traits of each species may be used for urban tree planting programs to ameliorate urban air pollution.     

Factors inhibiting nitrification of ammonia in deep wastewater reservoirs

Nitrification of ammonia in wastewater reservoirs is very slow, in spite of the ubiquitous presence of nitrifying bacteria. In an attempt to identify the reasons, the effect of several factors on the rate of nitrification and viability of N. europaea was studied. Light, NH₂OH and NH₂NH₂ were found to be inhibitory to exponentially growing cells of Nitrosomonas europaea, while ammonia provided limited protection. Stationary phase cells were unaffected by light. Water samples from two wastewater reservoirs had a variable effect upon viability and nitrification of laboratory cultures of N. europaea upon illumination, while long-term incubation of N. europaea cells placed in semi-permeable containers at different depths in the reservoirs had generally no effect on their viability.     

Enrichment of a K-strategist microbial population able to biodegrade p-nitrophenol in a sequencing batch reactor

The biological treatment of a high-strength p-nitrophenol (PNP) wastewater in an aerobic Sequencing Batch Reactor (SBR) has been studied. A specific operational strategy was applied with the main aim of developing a K-strategist PNP-degrading activated sludge. The enrichment of a K-strategist microbial population was performed using a non-acclimated biomass coming from a municipal WWTP as inoculum, and following a feeding strategy in which the PNP-degrading biomass was under endogenous conditions during more than 50% of the aerobic reaction phase. Hundred per cent of PNP removal was achieved in the whole operating period with a maximum specific PNP loading rate of 0.26 g PNP g⁻¹ VSS d⁻¹. A kinetic characterization of the obtained PNP-degrading population was carried out using respirometry assays in specifically designed batch tests. With the experimental data obtained a kinetic model including substrate inhibition has been used to describe the time-course of the PNP concentration and specific oxygen uptake rate (SOUR), simultaneously. The kinetic parameters obtained through optimization, validated with an additional respirometric test, were k_max = 1.02 mg PNP mg⁻¹ COD d⁻¹, K_s = 1.6 mg PNP L⁻¹ and K_i = 54 mg PNP L⁻¹. The values obtained for the K_s and k_max are lower than those reported in the literature for mixed populations, meaning that the biomass is a K-strategist type, and therefore demonstrating the success of the operational strategy imposed to obtain such a K-strategist population. Moreover, our measured K_i value is higher than those reported by most of the bibliographic references; therefore the acclimated activated sludge used in this work was evidently more adapted to PNP inhibition than the other reported cultures.     

Correlation between tension softening relation and crack extension resistance in concrete

Changes of the material fracture toughness with crack propagation can be described by a crack extension resistance curve, one of the fundamental fracture criteria in crack mechanics. Recently, experimental observation of the fracture behavior in concrete was used to develop a new fracture criterion, the crack extension G _R resistance curve, to analyze crack propagation during the entire concrete fracture process. The variation of the crack extension resistance is mainly associated with the energy consumption in the fracture process zone ahead of the stress-free crack tip. The crack extension resistance is then a function of the softening curve, which is a basic mechanical property in the fracture process zone. The relationship between the softening curve and the crack extension G _R resistance curve is then analyzed based on results of three-point bending beams tests. The results indicate that the characteristic points of the crack extension resistance G _R curve is closely related to the characteristic point on used tension softening curve. __________ Translated from Journal of Tsinghua University (Science and Technology), 2008, 48(3): 316–320 [译自: 清华大学学报(自然科学版)]     

Robust control of plate vibration via active constrained layer damping

In this paper, the theoretical modeling of a plate partially treated with active constrained layer damping (ACLD) treatments and its vibration control in an H_∞ approach is discussed. Vibration of the flat plate is controlled with patches of ACLD treatments, each consisting of a viscoelastic damping layer which is sandwiched between the piezo-electric constrained layer and the host plate. The piezo-electric constrained layer acts as an actuator to actively control the shear deformation of the viscoelastic damping layer according to the vibration response of the plate excited by external disturbances. In the first part of this paper, the Mindlin–Reissner plate theory is adopted to express the shear deformation characteristics of the viscoelastic damping layer, meanwhile GHM (Golla–Hughes–McTavish) model of viscoelastic damping material and FEM (finite element model) are incorporated to describe the dynamics of the plate partially treated with ACLD treatment. In the second part, particular emphasis is placed on the vibration control of the first four modes of the treated plate using H_∞ robust control method. For this purpose, an H_∞ robust controller is designed to accommodate uncertainties of the ACLD parameters, particularly those of the viscoelastic damping core which arise from the variation of the operation temperature and frequency. Disturbances and measurement noise are rejected in the closed loop by H_∞ robust controller. In the experimental validation, external disturbances of different types are employed to excite the treated plate. The results of the experimental clearly demonstrate that the proposed modeling method is correct and the ACLD treatments are very effective in fast damping out the structural vibration as compared to the conventional passive constrained layer damping (PCLD).     

The fate of chlorine in recirculating cooling towers Field results

Chlorine and chloramines are volatile compounds which are stripped (“flashed off”) from recirculating cooling water systems by the large volumes of air which flow through the water in the cooling tower. The fraction of a volatile gas, such as hypochlorous acid (HOCl), which is removed by stripping is determined by Henry's constant H for that gas: H = X_G/X_L, where X_G is the mole fraction of the gas in the air and X_L is the mole fraction of the gas in the water. We have measured H for HOCl, OCl⁻, NH₃, NH₂Cl, NHCl₂ and NCl₃ at 20 and 40°C. We found H = 0.076 for HOCl, compared to 0.71 for NH₃, at 20°C. At 40°C, H was about 2.5-fold larger for HOCl. This means that 10–15% of the HOCl is stripped from cooling water on each passage through a typical cooling tower. The measured flashoff of free available chlorine (HOCl + OCl⁻) was markedly pH-sensitive with a pK of 7.5, exactly as expected if HOCl is volatile but OCl⁻ is not. The data permit a quantitative understanding of the fate of chlorine in cooling systems. The values of H at 40°C for NH₂Cl, NHCl₂ and NCl₃ were 1.28, 3.76 and 1067. This means that all of the chloramines are quickly stripped in a cooling tower.     

Comparison between the short-term and the long-term toxicity of six triazine herbicides on photobacteria Q67

The bioluminescence inhibition of six triazine herbicides including desmetryne (DES), simetryn (SIM), velpar (VEL), prometon (PRO), metribuzin (MET), and aminotriazine (AMI) on Vibrio qinghaiensis sp.-Q67 (Q67) was determined to investigate the effects of exposure duration on the ecotoxicological relevance of triazine herbicides. Based on the short-term microplate toxicity analysis (MTA), a long-term MTA was established to assess the impact of exposure time on the toxicities of the herbicides. The results show that the long-term toxicities of DES and SIM are similar to their short-term toxicities, and the long-term toxicities of VEL, PRO, and MET are higher than their short-term toxicities, while AMI without short-term toxicity has a high long-term toxicity. In addition, a parabolic relationship was found between the pEC₅₀ (the negative logarithm of the EC₅₀, log 1/EC₅₀) and the logarithm of octanol-water partition coefficient (logK_ow). To better understand their toxicity process, the time-dependent toxicities of the six herbicides on Q67 were determined over a period of 12 h during which measurements were taken every 30 min to generate an integral effect surface related to both concentration and duration.     

Uptake and release of zinc by aquatic bryophytes (Fontinalis antipyretica L. ex. Hedw.)

The zinc uptake and posterior release by an aquatic bryophyte—Fontinalis antipyretica L. Ex Hedw.—was experimentally studied in laboratory exposing the plants to different zinc concentrations in the range, 1.0–5.0 mg l⁻¹, for a 144 h contamination period, and then exposed to metal-free water for a 120 h decontamination period. The experiments were carried out in perfectly mixed contactors at controlled illumination, using mosses picked out in February 1997, with a background initial zinc concentration of 263 mg g⁻¹ (dry wt.). A first-order mass transfer kinetic model was fitted to the experimental data to determine the uptake and release constants, k₁ and k₂, the zinc concentration in mosses at the end of the uptake period, C_mu, and at the equilibrium, for the contamination and decontamination stages, C_me and C_mr, respectively. A bioconcentration factor, BCF=k₁/k₂ (zinc concentration in the plant, dry wt./zinc concentration in the water) was determined. A biological elimination factor defined as BEF=1−C_mr/C_mu was also calculated. BCF decreases from about 4500 to 2950 as Zn concentration in water increases from 1.05 to 3.80 mg l⁻¹. BEF is approximately constant and equal to 0.80. Comparing Zn and Cu accumulation by Fontinalis antipyretica, it was concluded that the uptake rate for Zn (145 h⁻¹) is much lower than for Cu (628 h⁻¹) and the amount retained by the plant decreased by a factor of about seven.     

Growth kinetics of the filamentous microorganism Sphaerotilus natans in a model system of a food industry wastewater

Bulking by Sphaerotilus natans has been attributed to several factors such as low dissolved oxygen in the aeration basin, wastes with high C:N ratios and phosphorus limitation; however, the occurrence of bulking has been reported in fruit, vegetable, meat and poultry wastewaters in which the ratio C:N is variable.Growth of S. natans was analyzed in a model system of a food industry wastewater (potato processing waste) that was characterized by HPLC determining that citric acid was the most important identified component. The effect of several carbon sources on S. natans growth was also studied; different C:N ratios were tested in a continuous culture system (chemostat). This strain grew in a mineral medium with citric acid as a sole carbon source, in spite of the contradictory results found in literature. Chemostat studies showed that the medium was carbon-limited when C:N ratios <19 mgCOD (mgN-NH₃)⁻¹. Monod kinetic growth coefficients, determined for this strain in chemostat were: maximum specific growth rate, μ_max=0.301 h⁻¹; Monod constant, K_S=4.6 mgCOD l⁻¹; true biomass growth yield, Y^T_X/S=0.490 mgVSS (mgCOD)⁻¹; endogenous decay rate, k_d=0.011 h⁻¹ and maintenance coefficient, m_S=0.022 mgCOD (mgVSS)⁻¹ h⁻¹. The obtained parameters were compared with literature data and the effect of glucose and citric acid as carbon sources was discussed; these parameters are useful in modeling the growth of S. natans in potato processing wastewaters (or in other effluents under carbon-limiting conditions) especially when citrate is the main component and can be used to control filamentous bulking by metabolic or kinetic selection.     

Sorption and transport of acetaminophen, 17alpha-ethynyl estradiol, nalidixic acid with low organic content aquifer sand

The sorption and transport of three pharmaceutical compounds (acetaminophen, an analgesic; nalidixic acid, an antibiotic; and 17α-ethynyl estradiol, a synthetic hormone) were examined by batch sorption experiments and solute displacement in columns of silica, alumina, and low organic carbon aquifer sand at neutral pH. Silica and alumina were used to represent negatively-charged and positively-charged fractions of subsurface media. Column transport experiments were also conducted at pH values of 4.3, 6.2, and 8.2 for the ionizable nalidixic acid. The computer program UFBTC was used to fit the breakthrough data under equilibrium and nonequilibrium conditions with linear/nonlinear sorption. Good agreement was observed between the retardation factors derived from column model studies and estimated from equilibrium batch sorption studies. The sorption and transport of nalidixic acid was observed to be highly pH dependent, especially when the pH was near the pK_a of nalidixic acid (5.95). Thus, near a compound's pK_a it is especially important that the batch studies be performed at the same pH as the column experiment. While for ionic pharmaceuticals, ion exchange to oppositely-charged surfaces, appears to be the dominant adsorption mechanism, for neutral pharmaceuticals (i.e., acetaminophen, 17α-ethynyl estradiol) the sorption correlated well with the K_ow of the pharmaceuticals, suggesting hydrophobically motivated sorption as the dominant mechanism.     

Stress redistribution and ground arch development during tunneling

Three-dimensional stress adjustment caused by tunneling is related with ground arching development. Investigating the development of ground arching by stress redistribution during tunneling is presented. A three-dimensional numerical simulation model was developed to gain understanding of adjustment of tunneling stress. Vertical stress adjustments σ_ZZ above the tunnel roof during tunneling are analyzed, using four different cover depths H and four lateral pressure coefficients K. Shift of the inflection points of σ_ZZ-depth curves above the tunnel roof during tunneling can be a reliable index to show the development of ground arching.     

Sorption of organics on clay and synthetic humic-clay complexes simulating aquifer processes

Sorption/partition of several organic solute (contaminants) of a wide range of hydrophobicities was studied on clay and on clay-humic complexes representing aquifer-soil systems. The role of the mineral and of the organic (humic) fractions was elucidated and a model considering both fractions in the sorption process was proposed. The adsorption constants on humic (organic fraction), K_∝, were 8–20 times higher than on “pure” clay, K_m. But with soils with low to medium organic fractions (ƒ_∝ < 0.05) the contribution of the clay mineral to adsorption was quite significant, in spite of the fact that half of the sorption sites on the mineral surface were blocked by the humic. In the range of very low organic content in aquifer soil a non-linear pattern going through a minimum is observed between the overall partition coefficient and soil-organic fraction, transforming to the familiar linear relationship at higher ƒ_∝s. Both the K_∝ and K_m followed the linear-free energy relationship to the octanol-water partition coefficient K_ow.