Fate of phthalate esters in landfill leachate under subcritical and supercritical conditions and determination of transformation products.

The hypothesis of this study is that the complex organic load of landfill leachate could be reduced by supercritical water oxidation (SCWO) in a single stage, but this operation could lead to the formation of some undesired by-products of phthalate esters (PAEs). In this context, the fate of selected PAEs, butyl benzyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP) and di-n-octyl phthalate (DNOP), was investigated during the oxidation of leachate under subcritical and supercritical conditions. Experiments were conducted at various temperatures (250-500 °C), pressures (10-35 MPa), residence times (2-18 min) and dimensionless oxidant doses (DOD: 0.2-2.3). The SCWO process decreased the leachate's chemical oxygen demand (COD) from 34,400 mg/L to 1,120 mg/L (97%). Removal efficiencies of DEHP and DNOP with longer chains were higher than BBP. The DEHP, DNOP and BBP compounds were removed in the range of -35 to 100%, -18 to 92%, and 28 to 36%, respectively, by the SCWO process. Many non-target PAEs were qualitatively detected in the raw leachate apart from the selected PAEs. Besides, 97% of total PAEs including both target and non-target PAEs was mineralized at 15 MPa, 300 °C and 5 min. Although PAEs were highly mineralized during SCWO of the leachate, aldehyde, ester, amide and amine-based phthalic substances were frequently detected as by-products. These by-products have transformed into higher molecular weight by-products with binding reactions as a result of complex SCWO process chemistry. It has also been determined that some non-target PAEs such as 1,2-benzenedicarboxylic acid bis(2-methylpropyl)ester and bis(2-ethylhexyl) isophthalate can transform to the DEHP. Therefore, the suggested pathway in this study for PAEs degradation during the SCWO of the leachate includes substitution and binding reactions as well as an oxidation reaction.

Downregulation of plasma microRNA-29c-3p expression may be a new risk factor for diabetic retinopathy.

BACKGROUND: Circulation miRNAs have emerged as new biomarkers for identifying and monitoring the microvascular complications of diabetes. The aim of this study is to evaluate the levels of five candidate miRNAs (miR-29c-3p, miR-18a, miR-31, miR-181 and miR-20a) in patients with diabetic retinopathy (DR) and their relationship with disease severity. METHODS: The study included 31 diabetes patients without DR (NDR group), 68 patients with DR (DR group) and 30 healthy controls (HC group). Twenty-five of patients with DR were proliferative DR (PDR group) and 43 were non-proliferative DR (NPDR group) patients. Metabolic parameters and serum vascular endothelial growth factor (VEGF) levels of all participants were measured. Circulating miRNAs levels were determined by quantitative real-time PCR. Fundus examinations of all patients were performed by a single ophthalmologist. RESULTS: VEGF levels were significantly higher in the NDR, and DR groups compared to HC group (P=0.011 and P=0.014, respectively). Plasma miR-29c-3p was downregulated in diabetic patients with retinopathy and without retinopathy. This downregulation was more prominent in diabetic patients without retinopathy compared to those with retinopathy (P=0.016). There was no significant difference in plasma levels of miR-18a, miR-20a, miR-18a and miR-31 between diabetic subjects with and without retinopathy (P>0.05). There was no correlation between DR severity and the levels of miRNAs (P>0.05). In multivariate logistic regression analysis, it was found that changes in plasma miR-29c-3p expression of diabetic patients increased DR risk independent of other risk factors. CONCLUSIONS: Plasma miR-29c-3p expression is downregulated in diabetic patients with and without retinopathy, and changes in this miRNA are an independent risk factor for the development of DR.

Comparison of advanced biological treatment and nature-based solutions for the treatment of pharmaceutically active compounds (PhACs): A comprehensive study for wastewater and sewage sludge.

Passing of pharmaceutical residues into environment in an uncontrolled manner as a result of continuous increase in drug consumption across the globe has become a threatening problem for the ecosystems and almost all living creatures. In this study, diclofenac (DCF), carbamazepine (CBZ), 17ß-estradiol (17ß-E2) and 17α-ethynylestradiol (EE2) belonging to different therapeutic classes were investigated simultaneously in advanced biological treatment and nature-based treatments during 12-months sampling campaign. In this context, behavior patterns of pharmaceutically active compounds (PhACs) throughout the both wastewater and sludge lines in advanced biological wastewater treatment plant (WWTP), wastewater stabilization pond (WSP) and constructed wetland (CW) were discussed in detail based on each treatment processes seasonally. Furthermore, statistically evaluated data obtained in full-scale WWTPs were compared with each other in order to determine the valid removal mechanisms of these pharmaceutical compounds. While DCF and CBZ were detected very intensively both in the wastewater and sludge lines of the investigated WWTPs, steroid hormones,17ß-E2 and EE2, were determined below the LOQ value in general. Annual average removal efficiencies achieved in studied WWTPs for DCF ranged between -23.3% (in CW) and 75.2% (in WSP), while annual average removal rates obtained for CBZ varied between -20.7% (in advanced biological treatment) and 10.0% (in CW). It has been found that DCF was highly affected by different wastewater treatment processes applied in the WWTPs compared to CBZ which showed extraordinary resistance to all different treatment processes. Although calculated in different rates for each compounds, biodegradation/biotransformation and sorption onto sewage sludge were determined as the main removal mechanisms for PhACs in plants. Although showed a similar behavior in the sludge dewatering unit (decanter) present in the advanced biological WWTP, quite different behaviors observed in the anaerobic digester for DCF (up to 15% decrease) and CBZ (up to 95% increase). Sorption and desorption behaviors of DCF and CBZ were also evaluated in the sludge treatment processes found in advanced biological WWTP. Percentages of originated extra annual average of pharmaceutical loads were calculated as 0.64% and 0.90% for DCF and CBZ, respectively in the advanced biological WWTP due to the sidestream caused by the sludge dewatering unit.

Advanced oxidation of landfill leachate: Removal of micropollutants and identification of by-products.

Landfill leachate contains several macropollutants and micropollutants that cannot be removed efficiently by conventional treatment processes. Therefore, an advanced oxidation process is a promising step in post or pre-treatment of leachate. In this study, the effects of Fenton and ozone oxidation on the removal of 16 emerging micropollutants including polycyclic aromatic hydrocarbons (PAHs), phthalates, alkylphenols and pesticides were investigated. The Fenton and ozone oxidation of the leachate were performed with four (reaction time: 20-90 min, Fe(II) dose: 0.51-2.55 g/L, H2O2 dose: 5.1-25.5 g/L and pH: 3-5) and two (ozonation time: 10-130 min and pH: 4-10) independent variables, respectively. Among these operating conditions, reaction time played more significant role (p-value < 0.05) in eliminating di-(2-Ethylhexyl) phthalate, 4-nonylphenol and 4-tert-octylphenol for both processes. The results showed that Fenton and ozone oxidation processes had a high degradation potential for micropollutants except for the PAHs including four and more rings. Removal efficiencies of micropollutants by ozone and Fenton oxidation were determined in the range of 5-100%. Although the removal efficiencies of chemical oxygen demand (COD) and some micropollutants such as phthalates were found much higher in the Fenton process than ozonation, the degradation products occurred during the Fenton oxidation were a higher molecular weight. Moreover, the oxidation intermediates for the both processes were found as mainly benzaldehyde, pentanoic acid and hydro cinnamic acid as well as derivatives of naphthalenone and naphthalenediol. Also, acid ester with higher molecular weight, naphthalene-based and phenolic compounds were detected in the Fenton oxidation.

Investigation of micropollutants removal from landfill leachate in a full-scale advanced treatment plant in Istanbul city, Turkey.

Although the levels of micropollutants in landfill leachate and municipal wastewater are well-established, the individual removal mechanisms and the fate of micropollutants throughout a landfill leachate treatment plant (LTP) were seldom investigated. Therefore, the determination of the removal efficiencies and the fates of micropollutants in a full-scale leachate treatment plant located in the largest city of Turkey were aimed in this study. Some important processes, such as equalization pond, bioreactor, ultrafiltration (UF) and nanofiltration (NF), are being operated in the treatment plant. Landfill leachate was characterized as an intense pollution source of macro and micropollutants compared to other water types. Chemical oxygen demand (COD), NH3, suspended solids (SS) and electrical conductivity (EC) values of the landfill leachate (and their removal efficiencies in the treatment plant) were determined as 18,656 ± 12,098 mg/L (98%), 3090 ± 845 mg/L (99%), 4175 ± 1832 mg/L (95%) and 31 ± 2 mS/cm (51%), respectively. Within the scope of the study, the most frequently and abundantly detected micropollutants in the treatment plant were found as heavy metals (8 ± 1.7 mg/L), VOCs (38 ± 2 µg/L), alkylphenols (9 ± 3 µg/L) and phthalates (8 ± 3 µg/L) and the overall removal efficiencies of these micropollutants ranged from -11% to 100% in the treatment processes. The main removal mechanism of VOCs in the aerobic treatment process has been found as the volatilization due to Henry constants greater than 100 Pa·m3/mol. However, the molecular weight cut off restriction of UF membrane has caused to less or negative removal efficiencies for some VOCs. The biological treatment unit which consists of sequential anoxic and oxic units (A/O) was found effective on the removal of PAHs (62%) and alkylphenols (87%). It was inferred that both NO3 accumulation in anoxic reactor, high hydraulic retention time (HRT) and sludge retention time (SRT) in aerobic reactor provide higher biodegradation and volatilization efficiencies as compared to the literature. Membrane processes were more effective on the removal of alkylphenols (60-80%) and pesticides (59-74%) in terms of influent and effluent loads of each unit. Removal efficiencies for Cu, Ni and Cr, which were the dominant heavy metals, were determined as 92, 91 and 51%, respectively and the main removal mechanism for heavy metals has thought to be coprecipitation of suspended solids by microbial biopolymers in the bioreactor and the separation of colloids during membrane filtration. Total effluent loads of the LTP for VOCs, semi volatiles and heavy metals were 1.0 g/day, 5.2 g/day and 1.5 kg/day, respectively. It has been concluded that the LTP was effectively removing both conventional pollutants and micropollutants with the specific operation costs of 0.27 $/(kg of removed COD), 0.13 $/(g of removed VOCs), 0.35 $/(g of removed SVOCs) and 2.6 $/(kg of removed metals).

Transfer of single dose of intravitreal injection of ranibizumab and bevacizumab into milk of sheep.

AIM: To investigate whether single-dose intravitreal injections of bevacizumab and ranibizumab transfer into milk. METHODS: This study included lactating 12 sheep and a single 3-month old suckling lamb of each sheep. Two groups consisting of 6 sheep and their lambs were constituted; the ranibizumab group and the bevacizumab group before the administration of intravitreal injections, blood and milk samples were obtained from all sheep and, following the injections, blood and milk samples of all sheep and blood samples of all lambs were collected at regular time points. Serum and milk concentrations of bevacizumab and ranibizumab were measured using an enzyme-linked immunosorbent assay (ELISA) kit. The limit of determination was 0.9 ng/mL for bevacizumab and 0.62 ng/mL for ranibizumab. RESULTS: At 6h after intravitreal injections, bevacizumab concentration was above the limit of determination in the blood of all sheep. At 3wk, when the study was terminated, bevacizumab concentrations were high in 4 sheep. Even though bevacizumab concentrations in milk showed fluctuations, the drug transferred into the milk of all sheep at detectable concentrations. Ranibizumab drug concentrations in the blood and milk of sheep and those in the blood of lambs were below the limit of determination by the ELISA kit. CONCLUSION: This sheep model study demonstrate that intravitreal injection of ranibizumab, which did not transfer into the milk of sheep and suckling lambs, is safer than bevacizumab during lactation period.

Corneal limbal sebaceous adenoma.

PURPOSE: The aim of this study was to describe a case of a corneal limbal sebaceous adenoma. METHODS: An 83-year-old male patient presented with a white solid nodular lesion covering most of the cornea of his right eye. The corneal lesion was removed totally. The corneal surface was reconstructed by amniotic membrane transplantation. RESULTS: The histopathological examination of the lesion revealed the presence of a sebaceous adenoma. A systemic examination revealed no other abnormalities. CONCLUSIONS: Sebaceous adenomas on the ocular surface are known to be very rare. To the best of our knowledge, this is the first case of a sebaceous adenoma located on the cornea, reported in the literature. It is of vital importance to make a differential diagnosis of sebaceous adenomas of the eyelid and conjunctiva with the Muir-Torre syndrome associated with visceral malignancies.

Bilateral traumatic globe luxation with optic nerve transection.

PURPOSE: The purpose of this study was to document clinical findings and management of a patient with bilateral globe luxation and optic nerve transection. MATERIALS AND METHODS: A 25-year-old female patient was admitted to the emergency department with bilateral traumatic globe luxation following a motor vehicle accident. RESULTS: Visual acuity testing showed no light perception. The right pupil was dilated and bilaterally did not react to light. The globes were bilaterally intact. A computed tomography scan revealed Le Fort type II fractures, bilateral optic nerve transection and disruption of all extraocular muscles. The globes of the patient were bilaterally reduced into the orbit. However, the patient developed phthisis bulbi in the right eye at month 3. CONCLUSION: Globe luxation presents a dramatic clinical picture, and may lead to the development of severe complications due to the concomitance of complete optic nerve dissection and multiple traumas. Even if the luxated globe is repositioned into the orbit, there is still an increased risk of the development of phthisis due to ischemia.

Activation of pine cone using Fenton oxidation for Cd(II) and Pb(II) removal.

This paper describes activation of pine cone with Fenton reagent and determines the removal of Cd(II) and Pb(II) ions from aqueous solution. Changes of the surface properties of adsorbent materials were determined by the FT-IR and SEM analysis after activation of pine cone. The effect of Fe(2+)/H(2)O(2) ratio, ORP, pH and contact time were determined. Different adsorption isotherms were also obtained using concentrations of heavy metal ions ranging from 0.1 to 150mgL(-1). The adsorption process follows pseudo-first-order reaction kinetics and follows the Langmuir adsorption isotherm. The study discusses thermodynamic parameters, including changes in Gibbs free energy, entropy, and enthalpy, for the adsorption of Cd(II) and Pb(II) on activated cone, and revealed that the adsorption process was spontaneous and exothermic under natural conditions. The maximum removal efficiencies were obtained as 91% and 89% at pH 7 with 90 and 105-min contact time for Cd(II) and Pb(II), respectively.

A new approach to modification of natural adsorbent for heavy metal adsorption.

This paper describes modification of a natural adsorbent with Fenton reagent and determines the removal of Cd(II) ions from aqueous solution. Changes of the surface properties of adsorbent materials were determined by the FT-IR analysis after the modification of pine bark. The effect of Fe2+/H2O2 ratio, ORP, pH, and contact time were determined. Different adsorption isotherms were also obtained using concentrations of Cd(II) ions ranging from 0.1 to 100 mg L(-1). The adsorption process follows pseudo-first-order reaction kinetics and follows the Langmuir adsorption isotherm. The paper discusses thermodynamic parameters, including changes in Gibbs free energy, entropy, and enthalpy, for the adsorption of Cd(II) on modified bark, and revealed that the adsorption process was spontaneous and exothermic under natural conditions. The maximum removal efficiency obtained was 97% at pH 7 and with a 90-min contact time (for 35 mg L(-1) initial concentration and a 2.5 g L(-1) solid-to-liquid ratio).

Use of clinoptilolite for the removal of nickel ions from water: kinetics and thermodynamics.

This paper describes the removal of Ni(II) ions from aqueous solutions using clinoptilolite. The effect of clinoptilolite level, contact time, and pH were determined. Different isotherms were also obtained using concentrations of Ni(II) ions ranging from 0.1 to 100 mg L(-1). The ion-exchange process follows second-order reaction kinetics and follows the Langmuir isotherm. The paper discusses thermodynamic parameters, including changes in Gibbs free energy, entropy, and enthalpy, for the ion-exchange of Ni(II) on clinoptilolite, and revealed that the ion-exchange process was spontaneous and exothermic under natural conditions. The maximum removal efficiency obtained was 93.6% at pH 7 and with a 45 min contact time (for 25 mg L(-1) initial concentration and a 15 g L(-1) solid-to-liquid ratio).

Heavy metal adsorption by modified oak sawdust: thermodynamics and kinetics.

This paper describes the adsorption of heavy metal ions from aqueous solutions by oak (Quercus coccifera) sawdust modified by means of HCl treatment. Our study tested the removal of three heavy metals: Cu, Ni, and Cr. The optimum shaking speed, adsorbent mass, contact time, and pH were determined, and adsorption isotherms were obtained using concentrations of the metal ions ranging from 0.1 to 100mgL(-1). The adsorption process follows pseudo-second-order reaction kinetics, as well as Langmuir and D-R adsorption isotherms. The paper discusses the thermodynamic parameters of the adsorption (the Gibbs free energy, entropy, and enthalpy). Our results demonstrate that the adsorption process was spontaneous and endothermic under natural conditions. The maximum removal efficiencies were 93% for Cu(II) at pH 4, 82% for Ni(II) at pH 8, and 84% for Cr(VI) at pH 3.