Biomonitoring of wastewaters in treatment plants using ciliates

The aim of this project has been to study and compare the ciliate populations present in roptating biological reactors treating three different wastewaters. Wastewaters chosen were a maize mill (nejayote), a sugarcane/ethyl alcohol plant (vinasses) and a recycled paper mill (whitewaters). The initial dissolved organic contents, measured as soluble chemical oxygen demand (COD) and biochemical oxygen demand in five days (BOD₅), were 2040±150 mg COD L^–1 and 585±5 mg BOD₅L^–1 for nejayote; 2000±20 mg COD L^–1 and 640±5 mg BOD₅ L^–1 for vinasses and 960±200 mg COD L^–1 and 120±10 mg BOD₅ L^–1 for whitewaters. Results obtained indicate that ciliated protozoa proliferated in the different chambers of each rotating biological reactor (RBR). Saprobity indices, as a quantitative evaluation parameter, indicate that there are no universal species of ciliates associated with specific BOD₅ concentrations. Therefore, the number of species of ciliates present in the effluent indicate qualitatively the efficiency of removal of pollution from the wastewaters during treatment in the rotating biological reactors.     

Treatment of industrial wastewater with two-stage constructed wetlands planted with Typha latifolia and Phragmites australis

Industrial wastewater treatment comprises several processes to fulfill the discharge permits or to enable the reuse of wastewater. For tannery wastewater, constructed wetlands (CWs) may be an interesting treatment option. Two-stage series of horizontal subsurface flow CWs with Phragmites australis (UP series) and Typha latifolia (UT series) provided high removal of organics from tannery wastewater, up to 88% of biochemical oxygen demand (BOD₅) (from an inlet of 420 to 1000 mg L⁻¹) and 92% of chemical oxygen demand (COD) (from an inlet of 808 to 2449 mg L⁻¹), and of other contaminants, such as nitrogen, operating at hydraulic retention times of 2, 5 and 7 days. No significant (P < 0.05) differences in performance were found between both the series. Overall mass removals of up to 1294 kg COD ha⁻¹ d⁻¹ and 529 kg BOD₅ ha⁻¹ d⁻¹ were achieved for a loading ranging from 242 to 1925 kg COD ha⁻¹ d⁻¹ and from 126 to 900 kg BOD₅ ha⁻¹ d⁻¹. Plants were resilient to the conditions imposed, however P. australis exceeded T. latifolia in terms of propagation.     

Evaluation of a lab-scale tidal flow constructed wetland performance: Oxygen transfer capacity, organic matter and ammonium removal

Oxygen transfer capacity and removal of ammonium and organic matter were investigated in this study to evaluate the performance of a lab-scale tidal flow constructed wetland. Average oxygen supply under tidal operation (350 g m⁻² d⁻¹) was much higher than in conventional constructed wetlands (<100 g m⁻² d⁻¹), resulting in enhanced removal of BOD₅ and NH₄⁺. Theoretical oxygen demand from BOD₅ removal and nitrification was approximately matched by the measured oxygen supply, which indicated aerobic consumption of BOD₅ and NH₄⁺ under tidal operation. When BOD₅ removal increased from 148 g m⁻² d⁻¹ to 294 g m⁻² d⁻¹, neither exhausted oxygen from the aggregate matrix during feeding period (111 g m⁻² d⁻¹) nor effluent dissolved oxygen (DO) concentration (2.8 mg/L) changed significantly, demonstrating that the oxygen transfer potential of the treatment system had not been exceeded. However, even though DO had not been exhausted, inhibition of nitrification was observed under high BOD loading. The loss of nitrification was attributed to excessive heterotrophic biofilm growth believed to induce oxygen transfer limitations or oxygen competition in thickened biofilms.     

Novel engineering controls to increase leachate contaminant degradation by refuse: From lab test to in situ engineering application

Here we provide direct evidence through a series laboratory and field-scale experiments using different age refuse to treat landfill leachate that aged refuse exhibits increased leachate contaminants removal ability with refuse stabilization time addition. Ten-years aged refuse showed best contaminant removal in a laboratory-scale test, removing 70.0% (8340.0-2540.0 mg/L) chemical oxygen demand (COD) and 75.0% (910.0-215.0 mg/L) ammonium-N, as well as removing 61.5-67.0% COD and 50.4-58.1% ammonium-N with variable COD (9948.0-12286.0 mg/L) and NH₃-N (780.0-1184.0 mg/L) in a field-scale test, respectively. When the 10-years aged refuse was disinfected by 20% NaClO (wt%), COD, biochemical oxygen demand (BOD₅), total nitrogen (TN), and ammonium-N removal showed a dramatic decrease throughout operation time from 84.4-86.2% to 15.2-34.5%, 94.4-99.8% to 26.2-54.4%, 31.2-33.9% to 2.1-10.1%, and 88.5-90.1% to 1.5-14.5%, respectively, suggesting biodegradation is the dominant contaminant removal. Based on this finding, a 3-stages (8 years) age refuse bioreactor (ARB) was constructed to treat leachate and ARB efficiently reduced chemical oxygen demand (COD) from 5478.0-10842.0 mg/L to 261.0-1020 mg/L (87.8-96.2% removal), ammonium-N from 811.4-1582.0 mg/L to 8.5-43.3 mg/L (96.9-99.4%), respectively, in 18 months running. In summary, the present studies suggest that increased leachate contaminant biodegradation ability of aged refuse could be used directly to create an engineering approach to treat leachate with operational and economic advantages.     

Water column oxygen demand and sediment oxygen flux: patterns of oxygen depletion in tidal creeks

Low dissolved oxygen (DO) levels often occur during summer in tidal creeks along the southeastern coast of the USA. We analyzed rates of oxygen loss as water-column biochemical oxygen demand (BOD₅) and sediment oxygen flux (SOF) at selected tidal creek sites monthly over a 1-year period. Ancillary physical, chemical and biological data were collected to identify factors related to oxygen loss. BOD₅ rates ranged from 0.0 mg l^?1 to 7.6 mg l^?1 and were correlated positively with organic suspended solids, total suspended solids, chlorophyll a concentrations, temperature, and dissolved oxygen, and negatively with pH and nitrate + nitrite. SOF rates ranged from 0.0 to 9.3 g O₂ m^?2 d^?1, and were positively correlated with temperature, chlorophyll a, and total suspended solids, but negatively with dissolved oxygen. Both forms of oxygen uptake were seasonally dependent, with BOD₅ elevated in spring and summer and SOF elevated in summer and fall. Average oxygen loss to sediments was greater and more variable than oxygen loss in the water column. Oxygen deficits at three of five locations were significantly related to BOD₅ and SOF, but not at two sites where ground water discharges were observed. Correlation and principal component analyses suggested that BOD₅ and SOF responded to somewhat different suites of environmental variables. BOD₅ was driven by a set of parameters linked to warm season storm water inputs that stimulated organic seston loads, especially chlorophyll a, while SOF behaved less strongly so. Runoff processes that increase loads of organic material and nutrients and ground water discharges low in dissolved oxygen contribute to occurrences of low dissolved oxygen in tidal creeks.     

Contaminant removal efficiency depending on primary treatment and operational strategy in horizontal subsurface flow treatment wetlands

This study aimed to evaluate the contaminant removal efficiency of shallow horizontal subsurface flow treatment wetlands (SSF TWs) as a function of (1) primary treatment (hydrolytic upflow sludge blanket (HUSB) reactor vs. conventional settling) and (2) operation strategy (alternation of saturated/unsaturated phases vs. permanently saturated). An experimental plant was constructed, operated and surveyed for the main water quality parameters over a period of 2.5 years. The plant had 3 treatment lines: a control line (settler-wetland permanently saturated), a batch line (settler-wetland operated with saturated/unsaturated phases) and an anaerobic line (HUSB reactor-wetland permanently saturated). In each line wetlands had a surface area of 2.80 m², a water depth of 25 cm and a granular medium D₆₀ = 7.3 mm, and were planted with common reed. During the study period the wetlands were operated at a hydraulic and organic load of 28.5 mm/d and about 4.7 g BOD/m² d, respectively. Effluent average redox potential was lower for the anaerobic line (−45 ± 78 mV) than for the other two lines (3 ± 92.7 and −5 ± 71 mV for control and batch, respectively). Overall, chemical oxygen demand (COD), biochemical oxygen demand (BOD₅) and ammonium mass removal efficiencies were slightly greater for the batch line (88%, 96% and 87%, respectively) than for the control line (83%, 94% and 80%) and the anaerobic line (80%, 87% and 73%). During cold seasons, COD and ammonium removal in the batch line was around 30% and 50% higher than in the control line, respectively. The results of this study indicate that the implementation of a HUSB reactor as primary treatment did not enhance the treatment capacity of the system (in comparison with a conventional settler). The efficiency of treatment wetland systems with horizontal subsurface flow can be improved using a batch operation strategy.     

A kinetic evaluation of anaerobic treatment of swine wastewater at two temperatures in a temperate climate zone

A static granular bed reactor (SGBR) was used to treat swine wastewater at 24 and 16 °C. At 24 °C, the organic loading rate (OLR) was 0.7-5.4 kg COD/m³ day and the average chemical oxygen demand (COD) removal efficiency was 88.5%, respectively. Meanwhile, at 16 °C, the OLR was 1.6-4.0 kg COD/m³ day and the average COD removal efficiency was 68.0%, respectively. The SGBR acted as a bioreactor as well as a biofilter. After backwashing, the recovery of COD removal was not a function of an OLR but recovery time, while that of TSS removal was not a function of either recovery time or the OLR. The maximum substrate utilization rate (k_max) ratio was 1.89 between 24 and 16 °C, and the half velocity constant (K_s) ratio was 1.22, and the maximum specific growth rate (μ_max) ratio was 4.71. In addition, the temperature-activity coefficient in this study was determined to be 1.09.     

Mountain cheese factory wastewater treatment with the use of a hybrid constructed wetland

This paper describes the activity period of an experimental hybrid wetland system placed in a cold climate region. The aim is to determine the efficiency of the system in reducing TSS, BOD₅, COD and other pollutants. The constructed wetland consists of a fat-removal unit and a basin for the storage and the distribution of the wastewater which precedes three phytoremediation beds: the first two are parallel and they work as submerged vertical flow wetland with gravel medium for an area of 180 m²; the last is a submerged horizontal flow wetland with sand medium and an area of 360 m². The CW was designed to process a total estimated BOD₅ loading rate of about 24 g m⁻² d⁻¹, which was less than half of the average actual loading rate. The wastewater treatment did not meet the required Italian law outflow limits, most likely due to BOD₅ overloading.     

Partial nitrification and nutrient removal in intermittently aerated sequencing batch reactors treating separated digestate liquid after anaerobic digestion of pig manure

The performance of an intermittently aerated sequencing batch reactor (IASBR) technology was investigated in achieving partial nitrification, organic matter removal and nitrogen removal from separated digestate liquid after anaerobic digestion of pig manure. The wastewater had chemical oxygen demand (COD) concentrations of 11,540 ± 860 mg/L, 5-day biochemical oxygen demand (BOD₅) concentrations of 2,900 ± 200 mg/L and total nitrogen (TN) concentrations of 4,041 ± 59 mg/L, with low COD:N ratios (2.9) and BOD₅:COD ratios (0.25). Synthetic wastewater, simulating the separated digestate liquid with similar COD and nitrogen concentrations but BOD₅ of 11,500 ± 100 mg/L, was also treated using the IASBR technology. At a mean organic loading rate of 1.15 kg COD/(m³ d) and a nitrogen loading rate of 0.38 kg N/(m³ d), the COD removal efficiency was 89.8% in the IASBR (IASBR-1) treating digestate liquid and 99% in the IASBR (IASBR-2) treating synthetic wastewater. The IASBR-1 effluent COD was mainly due to inert organic matter and can be further reduced to less than 40 mg/L through coagulation. The partial nitrification efficiency of 71–79% was achieved in the two IASBRs and one cause for the stable long-term partial nitrification was the intermittent aeration strategy. Nitrogen removal efficiencies were 76.5 and 97% in IASBR-1 and IASBR-2, respectively. The high nitrogen removal efficiencies show that the IASBR technology is a promising technology for nitrogen removal from low COD:N ratio wastewaters. The nitrogen balance analysis shows that 59.4 and 74.3% of nitrogen removed was via heterotrophic denitrification in the non-aeration periods in IASBR-1 and IASBR-2, respectively.     

Bimetallic copper(II) and zinc(II) complexes of acyclic Schiff base ligands derived from amino acids

The acyclic Schiff-base ligands (2-(OH)-5-(R³)C₆H₂-1,3-(HCNC(R¹)(R²)CO₂H), derived from the dialdehyde 2-hydroxy-5-R-1,3-benzenedicarboxaldehyde (R = Me or t-Bu) and two equivalents of the amino acids glycine, 2,2-diphenylglycine or phenylalanine, have been reacted with the metal acetates M(OAc)₂ (M = Cu, Zn) in the presence of triethylamine, affording the complexes [HNEt₃][M₂(CH₃CO₂)₂(2-(O)-5-(t-Bu)C₆H₂-1,3-(HCNC(R¹)(R²)CO₂)₂] (M = Cu, R¹ = R² = C₆H₅, R³ = Me (1); M = Zn, R¹ = R² = H, R³ = t-Bu (2); M = Zn, R¹ = R² = C₆H₅, R³ = t-Bu (3); M = Zn, R¹ = H, R² = CH₂C₆H₅, R³ = t-Bu (4)) in good yields. The crystal structures of 1·MeCN, 2·, 3·2MeOH, and 4·3MeOH have been determined.     

Polishing low-biodegradable and saline industrial effluent in a full-scale horizontal subsurface flow constructed wetland: evaluation of bio-treatability and predictive power of kinetic models

Abstract

This study evaluates the bio-treatability performance and kinetic models of full-scale horizontal subsurface flow constructed wetland used for the tertiary treatment of composite industrial effluent characterized by high-salt content ranging from 5830 to 10,400 µS/cm and biochemical oxygen demand (BOD₅): chemical oxygen demand (COD) ratio below 0.2. The wetland vegetated with Phragmites australis was operated in a semi-arid climate under an average hydraulic loading rate of 63?mm/d. The results of a 4-year operation calculated based on the concentration of pollutants showed that the average removal efficiency of COD, BOD_5, and total suspended solids (TSS) were 17.5, 5.1, and 11.2%, respectively. The system reduced up to 6.5?±?0.7% of electrical conductivity presenting poor phyto-desalination potential without considering the contribution of evapotranspiration in water balance in contrast to satisfying performance for heavy metals reduction. The comparison of the kinetics of organic matter removal obtained by the first-order and Monod models paired with continuous stirred-tank reactor and plug flow regime showed that Monod-plug flow model provided the best fit with the constants of 2.01?g COD/m²·d and 0.3014?g BOD₅/m²·d with the best correlation coefficient of 0.610 and 0.968 between the predicted and measured concentrations, respectively. The low kinetic rates indicate that the process is capable of effluent polishing instead of purification due to the presence of organic compounds recalcitrant to biodegradation and a high level of salinity.     

Coupling of anodic biooxidation and cathodic bioelectro-Fenton for enhanced swine wastewater treatment

A novel bioelectrochemical reactor with anodic biooxidation coupled to cathodic bioelectro-Fenton was developed for the enhanced treatment of highly concentrated organic wastewater. Using swine wastewater as a model, the anode-cathode coupled system was demonstrated to be both efficient and energy-saving. Without any external energy supply to the system, BOD₅, COD, NH₃-N and TOC in the wastewater could be greatly reduced at both 1.1 g COD L⁻¹ d⁻¹ and 4.6 g COD L⁻¹ d⁻¹ of OLR, with the overall removal rates ranging from 62.2% to 95.7%. Simultaneously, electricity was generated at around 3-8 W m⁻³ of maximum output power density. Based on electron balance calculation, 60-65% of all the electrons produced from anodic biooxidation were consumed in the cathodic bioelectro-Fenton process. This coupled system has a potential for enhanced treatment of high strength wastewater and provides a new way for efficient utilization of the electron generated from biooxidation of organic matters.     

Study on ecological protection and rehabilitation technology of a reservoir-type water source in the northeastern region of China

ABSTRACT

Surface water is the main source of water for human life and production. The quality of water affects living conditions and the overall health of people. Ecological protection and restoration engineering technology, combining ecological revetment and an ecological floating bed, is applied to a selected shallow beach experimentation area of a reservoir water source area in Northeast China. According to local conditions, the ecological revetment plants were identified as Goosegrass, sedges, and water grasses, and other local species of Polygonum hydropiper bagen, reeds, and bulrushes were identified as ecological floating bed plants. Regular monitoring of water quality in the experimentation area and a control area showed that the ecological protection and restoration technology can effectively reduce the concentrations of BOD₅ (five day biochemical oxygen demand), COD (chemical oxygen demand), TN, NH₃-N, NO₃^?-N, TP, TDP, Mn, Zn, Fe, Pb, total coliforms, and other indicators of surface water in the experimentation area. The BOD₅, COD, Max TN, NH₃-N, NO₃^?-N, TP, and TDP reduction rates were 84.76%, 57.14%, 86.76%, 83.78%, 89.26%, 94.02%, and 95.89%, respectively, with the implementation of water pollution prevention and the purifying shoal.     

Electrochemical oxidation of methanol using alcohol-soluble Ru/Pt and Ru/Pd catalysts

The heterobimetallic Ru/Pt and Ru/Pd complexes [η⁵-C₅H₄CH₂CH₂N(CH₃)₂ · HI]Ru(PPh₃)(μ-I)(μ-dppm)PtCl₂ (7), [η⁵-C₅H₄CH₂CH₂N(CH₃)₂ · HI]Ru(PPh₃)(μ-I)(μ-dppm)PtI₂ (8), [η⁵-C₅H₄CH₂CH₂N(CH₃)₂ · HI]Ru(PPh₃)(μ-I)(μ-dppm)PdCl₂ (9), and [η⁵-C₅H₄CH₂CH₂N(CH₃)₂ · HI]Ru(PPh₃)(μ-I)(μ-dppm)PdI₂ (10) were prepared by the reaction of [η⁵-C₅H₄CH₂CH₂N(CH₃)₂ · HI]Ru(PPh₃)I(κ¹-dppm) (6) with Pt(COD)Cl₂, Pt(COD)I₂, and Pd(COD)Cl₂, respectively. Electronic interaction between the two metals is significant for the iodide-bridged compounds 7-10, as evidenced by the shifts of their redox potentials in comparison to the mononuclear complexes. The electrochemical oxidation of methanol was carried out with heterobimetallic complexes 7-10 and leads to the formation of dimethoxymethane (DMM) and methyl formate (MF) as the major oxidation products. The chloride complexes 7 and 9 are the most active catalysts, as evidenced by their TON and current efficiencies. Addition of water at the beginning of the electrolysis results in increased formation of the more oxidized product MF along with higher current efficiencies and TON.     

Unusual hexamers and infinite water chains trapped in the complexes of 2-(4-pyridyl)benzimidazole

Unusual hexamers and water chains have been observed in the complexes of (HPyBIm)⁺(Hterephate)⁻(PyBIm) · 4H₂O (1) and [Ag₂(PyBIm)₂(μ₂-SO₄)] · 4H₂O (2), respectively (PyBIm = 2-(4-pyridyl)benzimidazole). In 1, a chair-shaped hexamer (not water hexamer) formed by the water molecules and carboxylate groups as well as one-dimensional water chain are being observed. While in 2, a water hexamer-shaped as parallelogram is obtained; more interestingly, the parallelogram-shaped water hexamers are further aggregated into tape like infinite water chain via hydrogen-bonding interactions.     

Study on potential antitumor mechanism of a novel Schiff base copper(II) complex: synthesis, crystal structure, DNA binding, cytotoxicity and apoptosis induction activity

A new cytotoxic copper(II) complex with Schiff base ligand [Cu^II(5-Cl-pap)(OAc)(H₂O)]·2H₂O (1) (5-Cl-pap = N-2-pyridiylmethylidene-2-hydroxy-5-chloro-phenylamine), was synthesized and structurally characterized by X-ray diffraction. Single-crystal analysis revealed that the copper atom shows a 4 + 1 pyramidal coordination, a water oxygen appears in the apical position, and three of the basal positions are occupied by the NNO tridentate ligand and the fourth by an acetate oxygen. The interaction of Schiff base copper(II) complex 1 with DNA was investigated by UV-visible spectra, fluorescence spectra and agarose gel electrophoresis. The apparent binding constant (K_app) value of 6.40 × 10⁵ M^− 1 for 1 with DNA suggests moderate intercalative binding mode. This copper(II) complex displayed efficient oxidative cleavage of supercoiled DNA, which might indicate that the underlying mechanism involve hydroxyl radical, singlet oxygen-like species, and hydrogen peroxide as reactive oxygen species. In addition, our present work showed the antitumor effect of 1 on cell cycle and apoptosis. Flow cytometric analysis revealed that HeLa cells were arrested in the S phase after treatment with 1. Fluorescence microscopic observation indicated that complex 1 can induce apoptosis of HeLa cells, whose process was mediated by intrinsic mitochondrial apoptotic pathway owing to the activation of caspase-9 and caspase-3.     

Ni(II) coordination compounds based on mixed phthalate and aromatic amine ligands: synthesis, crystal structures and magnetic properties

Three new coordination compounds, [Ni(Pht)(Py)₂(H₂O)₃] (1), [Ni(Pht)(β- Pic)₂(H₂O)₃] · H₂O (2) and [Ni(Pht)(1-MeIm)₂(H₂O)₃] (3) (where Pht²⁻ = dianion of o-phthalic acid; Py = pyridine, β-Pic = 3-methylpyridine, 1-MeIm = 1-methylimidazole), have been synthesized and characterized by IR spectroscopy and thermogravimetric analysis. Crystallographic studies 1-3 reveal that each Ni(II) center has a distorted octahedral geometry being coordinated by two nitrogen atoms of aromatic amines, one oxygen atom from a carboxylate group of a phthalate ligand and three water molecules. Pht²⁻ anions act as monodentate ligands, while the remaining uncoordinated carboxylate oxygen atoms participate in the formation of hydrogen bonding. The uncoordinated oxygen atoms form hydrogen bonds with the coordinated water molecules from adjacent complexes creating a centrosymmetric dimer unit. Further, these dimer units are connected by O-H?O hydrogen bonds in double-chains. Depending on the nature of aromatic amines, the arrangement of these double-chains differs. The double-chains are held together only by van der Waals interactions in 1. In contrast, in 2 these chains form layers by π-π interactions between antiparallel molecules of β-Pic as well as by π-π interactions between β-Pic and Pht aromatic rings. In complex 3, the double-chains are knitted together via C-H?O hydrogen bonds between the methyl group of 1-MeIm and the coordinated carboxylate oxygen atom of Pht, as well as π-π contacts involving antiparallel 1-MeIm cycles. The thermal dependence of the magnetic susceptibilities for compounds 1 and 2 shows a weak antiferromagnetic interaction between the two Ni²⁺ ions of the hydrogen bonded dimers. For compound 3, a ferromagnetic interaction could be observed. Modeling the experimental data with MAGPACK resulted in: g = 2.22, |D| = 4.11 cm⁻¹ and J = −0.29 cm⁻¹ for compound 1, g = 2.215, |D| = 3.85 cm⁻¹ and J = −0.1 cm⁻¹ for compound 2 and g = 2.23, |D| = 4.6 cm⁻¹ and J = 0.22 cm⁻¹ for compound 3.     

Stability and efficiency of biofilms for landfill leachate treatment

The objective of this work was to assess the feasibility of a fixed-film biological aerated filtration process for the treatment of the leachate produced at Harnhill landfill site (South Gloucestershire, UK). The laboratory scale plant consisted of four identical biological aerated filters (a triplicate and a “control” column) packed with small brick fragments. Biofilm formed within 24 h of immersion of the support material in the reactor, and had a high resistance to antibiotics and other toxic agents. The plant maintained a stable operation in the 20–45 °C temperature range, showing the best results (35.4 ± 6.6% COD removal and 73.9 ± 5.5% BOD₅ reduction) at 40 °C. The lowest COD and BOD₅ values obtained at the outlet of the columns were 7067 mg/L and 1050 mg/L, respectively.