Microplastics and organics - A comparative study of sorption of triclosan and malachite green onto polyethylene.

This study aims to elucidate interaction of organics with microplastics in a comparative manner via the use of two model compounds (i.e., triclosan (TCS) and malachite green (MG)) having different physicochemical properties, onto polyethylene (PE). TCS, is hydrophobic with low solubility, while MG is hydrophilic with high aqueous solubility. Kinetic studies indicate faster sorption (teq = 24 h) and equilibrium studies show much higher capacity (qe = 6,921 µg/g) for TCS, when compared to those of MG (teq = 5 d, qe = 221 µg/g). While pseudo-kinetic model fits sorption of both organics to PE, equilibrium isotherms as well as the results on effect of particle size and pH indicate dissimilar sorption mechanisms. Considering pHPZC = 2, observation of favourable sorption of TCS in acidic regions and sorption being unaffected by particle size was explained by TCS sorption to be dominated by hydrophobic interactions in amorph regions of PE. Higher removal of MG was observed at lower surface charge of PE, and a clear favourable impact of surface area on MG sorptive capacity pointed to the presence of non-specific van der Waals type interactions on the surface of PE. Mechanistic evaluations presented here contribute to our understanding of interaction of MPs with organics in aquatic ecosystems.

Sewage sludge as a source of microplastics in the environment: A review of occurrence and fate during sludge treatment.

Modern wastewater treatment plants (WWTPs) effectively remove microplastics (MPs) from wastewater and unsurprisingly concentrate them in sludge. Hence through its beneficial use and disposal, sludge causes secondary release pathways of an estimated average amount of 106 to 1014 wastewater-based MPs to various environmental compartments yearly. Despite these numbers, studies investigating sludge are scarce. Currently, majority of the studies in the field focus on identifying the magnitude of the problem, whereas research investigating the fate and effects of MPs during sludge treatment are very rare. This review aims to bring together and critically evaluate the limited studies conducted about MPs in the sludge treatment line and bring out the key gaps and research needs in the area. Studies conducted so far indicate that depending on the type, size, and amount of MPs, their effects during anaerobic digestion differ, with some studies demonstrating serious negative impact on biogas production. Possible effect mechanisms are also suggested such as formation of reactive oxygen species (ROS) and leaching of toxic chemicals. Moreover, a potential for sludge treatment processes (thickening, dewatering, drying, stabilization, etc.) to change the characteristics and the number of MPs, which may increase surface area available for adsorption and desorption of pollutants, was observed. Review uncovers that, in the broad universe of MPs, some highly abundant ones in sludge such as polypropylene, polyurethane, polycarbonate, and acrylic are not yet investigated in sludge treatment. Future research should focus not only to investigate the fate/effects but to fully understand the mechanisms behind these, which is missing in many studies reviewed. Besides, new studies show that effect of MPs start from the floc formation stage during biological treatment, which in fact determine the final sludge behavior in thickening and dewatering. Therefore, holistic approaches starting from wastewater till sludge exits WWTP seem necessary. Substantiating from polymer chemistry and response of plastics to stress conditions, review suggests possibilities of deterioration during sludge treatment processes. It becomes evident that some totally uninvestigated aspects such as disintegration conducted before stabilization, can change the fate of MPs during sludge treatment and may bring new perspectives to the solution of the problem.

Effects of anaerobic digestion enhanced by ultrasound pretreatment on the fuel properties of municipal sludge.

In this study, effects of ultrasound pretreatment on combustion characteristics and elemental composition of municipal sludge were examined for energy-based evaluation of sludge pretreatment. Waste activated sludge (WAS) from a municipal wastewater treatment plant was pretreated with ultrasound at varying durations and was subjected to anaerobic digestion in a biochemical methane potential (BMP) assay. Changes in gas production rates, calorific value (CV), elemental compositions, and ash contents of sludge samples were examined to assess the effects of pretreatment and digestion. Sonication at 0.73 W/mL enhanced gas production by 28%. Moreover, volatile solids (VS) and chemical oxygen demand (COD) removals increased from 41 to 45% and 33 to 37%, respectively. Following anaerobic digestion, CVs of samples decreased by about 18%. Sonicated samples exhibited a higher decrease. In order to quantify the change in overall energy content, total solids (TS) reduction was also taken into account. Loss was magnified as both CV and the amount of TS that would provide the overall energy were reduced. This loss was 38% for the control group and 41% for the 15 min sonicated sludge. Digestion decreased the C content of sludge by about 20% and H content by 50% due to biogas production. Ash content increased relatively as some of the combustible solids were lost due to digestion. Experimental results indicate that if sludge is to be combusted, digestion with or without ultrasound pretreatment may be disadvantageous if the aim is to maximize energy gain from sludge.

A comparative evaluation of anaerobic dechlorination of PCB-118 and Aroclor 1254 in sediment microcosms from three PCB-impacted environments.

Aroclor 1254 (A1254) is the most toxic commercial PCB mixture produced, primarily due to its relatively high concentrations of dioxin-like congeners. This study demonstrates a comparative evaluation of dechlorination of A1254 and PCB-118 by indigenous organohalide respiring bacteria enriched from three PCB impacted sites: Grasse River (GR), NY; Fox River (FR), WI; and Baltimore Harbor (BH), MD. PCB-118 dechlorination rates in GR, BH, and FR was 0.0308, 0.015, and 0.0006 Cl-/biphenyl/day, respectively. A1254 dechlorination rates in GR, FR, and BH were 0.0153, 0.0144, and 0.0048 Cl-/biphenyl/day, respectively. A1254 dechlorination was achieved through the removal of doubly-/singly-flanked chlorines in meta and para positions of mostly penta- followed by hexa- and hepta-chlorinated congeners by 88%, 69%, and 51% in GR, and 88%, 87%, and 83% in FR, respectively, while in BH mostly hepta- (70%) followed by hexa-chlorinated congeners (66%) were dechlorinated. A previously developed Anaerobic Dechlorination Model (ADM) quantified a total of 17 toxicity-related dechlorination pathways in all three sediment microcosms. The toxic equivalency of A1254 based on seven dioxin-like congeners decreased by about 53%, 45% and 21%, in GR, FR and BH microcosms, respectively. The dechlorination products were generally tetra- and tri-chlorinated congeners with unflanked chlorines, all of which is susceptible to further degradation by aerobic bacteria. Concerning the toxic congeners, ADM can be useful to initiate further research focusing on the stimulation of the toxicity reducing pathways for risk assessment and effective remediation strategies.

Potential risk reduction of Aroclor 1254 by microbial dechlorination in anaerobic Grasse River sediment microcosms.

Aroclor 1254 was the second most produced commercial PCB mixture and is found in soils, sediments and sewage throughout the globe. This commercial PCB mixture is considered particularly toxic because of the relatively high concentrations of congeners with dioxin-like properties. The potential for risk reduction by microbial reductive dechlorination of Aroclor 1254 (A1254) was investigated in sediment microcosms from Grasse River (GR), Massena, NY. The specificity of A1254 dechlorination was doubly- and singly-flanked chlorines in meta positions and to a less extent doubly-flanked para chlorines of 2345-substituted chlorobiphenyl rings. The average dechlorination rate of A1254 was 0.0153 Cl-/biphenyl/day, and dechlorination rates of single congeners ranged between 0.001 and 0.0074 Cl-/biphenyl/day. Potential risk associated with A1254 based on the toxic equivalency factors of the dioxin-like congeners was reduced by 83%. Additional potential risk associated with bioaccumulation in fish was reduced by 35% based on biota-sediment accumulation factor estimates for all detected congeners. Finally, the dechlorination end-products were tri- and tetra-chlorobiphenyls with unflanked chlorines, all of which are susceptible to further degradation by aerobic microorganisms. The combined results indicate that microbial reductive dechlorination has the potential for reducing risk associated with toxicity and bioaccumulation in fish in sites contaminated with A1254.

Guluronic acid content as a factor affecting turbidity removal potential of alginate.

Alginates are natural polymers composed of mannuronic and guluronic acid residues. They are currently extracted from brown algae; however, alginate can also be synthesized by some species of Azotobacter and Pseudomonas. Alginates with different proportion of mannuronic and guluronic acids are known to have different characteristics and form gels at different extents in the presence of calcium ions. The aim of this work was to investigate the usefulness of alginate as a non-toxic coagulant used in purification of drinking water. This study utilized alginates from Azotobacter vinelandii having different guluronic acid levels. These were obtained partly by changing the cultivation parameters, partly by epimerizing a purified alginate sample in vitro using the A. vinelandii mannuronan C-5 epimerase AlgE1. The different alginates were then used for coagulation together with calcium. The results showed that turbidity removal capability was dependent on the content of guluronic acid residues. For the best performing samples, the turbidity decreased from 10 NTU to 1 NTU by the use of only 2 mg/L of alginate and 1.5 mM of calcium chloride.

Evaluation of solar sludge drying alternatives by costs and area requirements.

Thermal drying is a common method to reach above 90% dry solids content (DS) in sludge. However, thermal drying requires high amount of energy and can be expensive. A greenhouse solar dryer (GSD) can be a cost-effective substitute if the drying performance, which is typically 70% DS, can be increased by additional heat. In this study feasibility of GSD supported with solar panels is evaluated as an alternative to thermal dryers to reach 90% DS. Evaluations are based on capital and O&M costs as well as area requirements for 37 wastewater treatment plants (WWTPs) with various sludge production rates. Costs for the supported GSD system are compared to that of conventional and co-generation thermal dryers. To calculate the optimal costs associated with the drying system, an optimization model was developed in which area limitation was a constraint. Results showed that total cost was minimum when the DS in the GSD (DS(m,i)) was equal to the maximum attainable value (70% DS). On average, 58% of the total cost and 38% of total required area were associated with the GSD. Variations in costs for 37 WWTPs were due to differences in initial DS (DS(i,i)) and sludge production rates, indicating the importance of dewatering to lower drying costs. For large plants, GSD supported with solar panels provided savings in total costs especially in long term when compared to conventional and co-generation thermal dryers.

PCBs in sludge: development of a practical extraction procedure and its application in an urban water resource recovery facility.

Sludges originating from water resource recovery facilities act as a sink for various contaminants including polychlorinated biphenyls (PCBs). Investigation of such pollutants provides detailed information about the pollutant burden of the region from which incoming wastewater is derived. However, the current extraction methods for PCBs in wastewater and sludge are both time- and solvent-consuming. Therefore, the purposes of this study were to develop a practical PCB extraction procedure and to monitor PCB levels in sludge originating from an urban water resource recovery facility (WRRF). Procedure applicability was shown by comparing the extraction results of certified reference materials with that of Soxhlet and by checking surrogate recovery. Diethyl ether, hexane, and hexane:acetone mixture were evaluated as the PCB extraction solvent; hexane was the most efficient solvent with the recovery results (89 to 102%) in an acceptable range of 70 to 130%. The PCB concentrations of the WRRF sludges were in the range of 3.6 ± 0.3 to 64.4 ± 9.3 µg/kg dry matter.

Investigation of nonylphenol and nonylphenol ethoxylates in sewage sludge samples from a metropolitan wastewater treatment plant in Turkey.

Nonylphenol ethoxylates (NPEOs) have drawn significant attention within the last decade for both scientific and legislative reasons. In Turkey, the Regulation Regarding the Use of Domestic and Urban Sludges on Land states a limit value for the sum of nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) as NPE (NPE=NP+NP1EO+NP2EO). Unfortunately a standard method for the determination of these chemicals has not been yet set by the authorities and no data exists about the concentrations of NP and NPEOs in sewage sludge in Turkey. The aim of this study is to propose simple and easily applicable extraction and measurement techniques for 4-n-nonylphenol (4-n-NP), NP, NP1EO and NP2EO in sewage sludge samples and investigate the year round concentrations in a Metropolitan Wastewater Treatment Plant (WWTP) in Turkey. Different extraction techniques and GC/MS methods for sewage sludge were tested. The best extraction method for these compounds was found to be ultrasonication (5 min) using acetone as the solvent with acceptable recovery of analytes suggested by USEPA and other studies. The optimized extraction method showed good repeatability with relative standard deviations (RSDs) less than 6%. The recovery of analytes were within acceptable limits suggested by USEPA and other studies. The limits of detection (LODs) were 6 µg kg(-1) for NP and NP1EO, 12 µg kg(-1) for NP2EO and 0.03 µg kg(-1) for 4-n-NP. The developed method was applied to sewage sludge samples obtained from the Central WWTP in Ankara, Turkey. The sum NPE (NP+NP1EO+NP2EO) was found to be in between 5.5 µg kg(-1) and 19.5 µg kg(-1), values which are in compliance with Turkish and European regulations.

Fate and degradation kinetics of nonylphenol compounds in aerobic batch digesters.

Nonylphenol (NP) compounds are toxic and persistent chemicals that are not fully degraded either in natural or engineered systems. Current knowledge indicates that these compounds concentrate in sewage sludge. Therefore, investigating the degradation patterns and types of metabolites formed during sludge treatment are important for land application of sewage sludge. Unfortunately, the information on the fate of nonylphenol compounds in sludge treatment is very limited. This study aims to investigate the biodegradation patterns of nonylphenol diethoxylate (NP2EO) in aerobic batch digesters. For this purpose, two NP2EO spiked and two control laboratory aerobic batch digesters were operated. The spiked digester contained 3 mg/L NP2EO in the whole reactor content. The compounds of interest (parent compound and expected metabolites) were extracted with sonication and analyzed by gas chromatography-mass spectrometry (GC-MS) as a function of time. Results showed that, following the day of spike, NP2EO degraded rapidly. The metabolites observed were nonylphenol monoethoxylate (NP1EO), NP and dominantly, nonylphenoxy acetic acid (NP1EC). The mass balance over the reactors indicated that the total mass spiked was highly accounted for by the products analyzed. The time dependent analysis indicated that the parent compound degradation and daughter product formation followed first order kinetics. The digester performance parameters analyzed (VS and COD reduction) indicated that the spike of NP2EO did not affect the digester performance.

Toxicity of nonylphenol diethoxylate in lab-scale anaerobic digesters.

Nonylphenol compounds have high commercial, industrial and domestic uses owing to their surface active properties. In addition to their toxic, carcinogenic and persistent characteristics; they have drawn the attention of scientists lately due to their endocrine disrupting properties. Their widespread use and disposal cause them to enter wastewater treatment systems at high concentrations. Since they are highly persistent and hydrophobic, they accumulate mostly on sludge. In this study using Anaerobic Toxicity Assay (ATA) tests, the toxicity of a model nonylphenol compound, nonylphenol diethoxylate (NP2EO), for anaerobic digestion of sludge was determined. The test bottles were dosed with NP2EO in acetone, with concentrations ranging from 1 mg L(-1) to 30 mg L(-1). During the tests, gas productions and compositions in terms of methane and carbon dioxide were monitored. To be able to judge about the fate, the target compounds were extracted from water and sludge and analyzed using GC/MS. The sludge samples used for assembling the reactors were found to contain NP and NP1EO but no NP2EO. After the assay was completed, all the NP2EO spiked into the live reactors was found to disappear. The increase seen in NP1EO and NP and further accumulation of NP in the system, indicated the conversion of NP2EO to these metabolites. On the other hand, no conversion was observed in abiotic reactors. Inhibition of NP2EO for anaerobic microorganisms was not observed throughout the tests considering the biogas production of the test reactors in comparison to the control reactors.

Effect of digester F/M ratio on gas production and sludge minimization of ultrasonically treated sludge.

Sludge pretreatment by mechanical, chemical or thermal methods before anaerobic digestion has been applied to increase the digestability of excess sludge. Pretreatment processes rely on their ability to disrupt cell membranes and to release organic materials from the cells into the aqueous phase. Pretreatment by mechanical disintegration has grown rapidly in recent years in parallel with the advances in technology. Ultrasonic sludge disintegration -one of the most commonly used mechanical pretreatment methods- enables the occurrence of cavitation bubbles for the break-up of microorganism cells to extract intracellular materials. The purpose of this study was to conduct disintegration experiments to optimize sonication parameters and to operate subsequent batch anaerobic digesters to examine the effect of food to microorganism ratio (F/M) in sonicated and unsonicated samples. Results showed that high sonication powers and longer treatment times were effective in sludge disintegration in terms of soluble chemical oxygen demand release. Sonicated sludge digested in batch reactors with higher initial F/M ratio caused higher methane generations, higher sludge reductions and had better dewatering characteristics.

Ultrasonic pretreatment and subsequent anaerobic digestion under different operational conditions.

In this study ultrasonic pretreatment was investigated in order to improve anaerobic digestion. First, the most effective sonication time was selected during the preliminary studies conducted on waste activated sludge samples. Then the optimal time selected was confirmed running batch anaerobic reactors. In the last part of the experiments, the effect of sonication was investigated for different operational conditions of semi-continuous digesters. Preliminary studies showed 15 min of sonication increased 50 mg/L initial soluble COD concentration up to a value of 2500 mg/L. Batch anaerobic digester results indicated that the increased soluble substrate improved anaerobic biodegradability concurrently, again with the maximal improvement observed for 15 min of sonication. Results from semi-continuous reactors indicated that at SRT of 15 days and OLR of 0.5 kg/m(3) d, ultrasonic pretreatment improved the daily biogas production, methane production and volatile solids reduction significantly when compared to control system. During the operation of reactors at 7.5 days of SRT, pretreatment helped to keep the reactors working. A simple economical analysis of the system was performed using the data obtained during the laboratory study.

Alkaline solubilization and microwave irradiation as a combined sludge disintegration and minimization method.

Commonly used pretreatment method of alkaline solubilization (using NaOH) and a relatively new technology of microwave (MW) irradiation (160 degrees C) were combined as a pretreatment method of waste activated sludge (WAS) in this study. First alkaline and MW pretreatment methods were examined separately, then their combination for different conditions was investigated in terms of their effect on COD solubilization, turbidity and capillary suction time (CST). For combined pretreatments, soluble COD to total COD ratio (SCOD/TCOD) of WAS increased from 0.005 (control) to 0.18, 0.27, 0.34 and 0.37 for combined methods of MW and pH-10, 11, 12 and 12.5, respectively. Deteriorated dewaterability due to alkaline pretreatment was also improved due to the incorporation of MW irradiation. Further, with small scale batch anaerobic reactors, pH-10, pH-12, MW (alone), MW+pH-10 and MW+pH-12 pretreated WAS samples were anaerobically digested. Highest total gas and methane productions were achieved with MW+pH-12 pretreatment with 16.3% and 18.9% improvements over control reactor, respectively. Finally the performance of MW+pH-12 pretreatment was examined with 2L anaerobic semi-continuous reactors for 92 days and compared to that of the control reactors. These reactors were operated at an SRT of 15 days. After steady state, 43.5% and 55% improvements were obtained in respective daily total gas and methane productions. TS, VS and TCOD reductions were improved by 24.9%, 35.4% and 30.3%, respectively based on a relative calculation with respect to control reactors. This way combined alkaline-microwave treatment proved to be an effective sludge minimization method. Pretreated digested sludge had 22% improved dewaterability than unpretreated digested sludge. Higher SCOD and NH(3)-N concentrations were measured in the pretreated digested sludge supernatant; however, PO(4)-P concentration did not increase much.

Phosphorus defficiency and sludge bulking.

Separation by settling is one of the most troublesome stages of an activated sludge process. A decrease in the efficiency of separation of microbial biomass from the treated effluent causes a decrease in the overall efficiency of the treatment plant. One of the most common problems in activated sludge systems to negatively influence the settleability is sludge bulking which can be defined as non-settling situation of microbial mass. The main objective of this study is to find out the effect of phosphorus deficiency on bulking of activated sludge. In order to achieve this aim, the effects of a strictly phosphorus limited environment was investigated by running 6 semi-continuous activated sludge reactors. Since the specific aim of the study is to identify the effects of magnesium and calcium ions on sludge bulking in a phosphorus deficient medium, 3 different magnesium and calcium concentrations (5, 10, 20 meq l(-1)) were studied. Laboratory scale reactors were fed with synthetic wastewater and operated at a sludge age of 8 days. Results showed that, phosphorus deficiency caused sludge bulking. Sludge samples examined under microscope showed that the floc structures from reactors fed with different cations are significantly different. To identify the differences, a series of chemical analyses were conducted on the sludge samples. In addition to that, sludge volume index (SVI) values were monitored on a daily basis. Next, the concentration of phosphorus in the feed medium was increased in two separate steps and the possibility to cure the sludge bulking problem was investigated. It was found that bulking of activated sludges due to phosphorus deficiency could be cured by the addition of phosphorus. For phosphorus deficient bulking in relation to the cations present in the system some mechanisms are suggested.

An investigation of heavy metal biosorption in relation to C/N ratio of activated sludge.

The effect of C/N ratio of activated sludge on heavy metal biosorption was investigated. Three sets of semi-continuous reactors with different feed C/N ratios (9, 21 and 43 mg COD/mg TKN) were set up. Sorption equilibrium tests have indicated that the biosorptive capacity of activated sludge was highly dependent on metal species and the C/N ratio. The increase in C/N ratio resulted in an increase in the Cd(II) sorption capacity of activated sludge whereas it decreased the Cu(II) sorption capacity. As for Zn(II), a different behavior was observed such that, the highest and lowest capacities have occurred at C/N ratio of 21 and 43, respectively. For Ni(II) biosorption, isotherm tests produced greatly scattered data; so, it was not possible to obtain any plausible result to indicate the relationship between maximum adsorptive capacity and C/N ratio. The accompanying release of Ca(II) and Mg(II) ions and also carbohydrates into the solution during biosorption have indicated that ion exchange mechanism was involved however, was not the only mechanism during the sorption process.

Use of Fenton oxidation to improve the biodegradability of a pharmaceutical wastewater.

The applicability of Fenton's oxidation to improve the biodegradability of a pharmaceutical wastewater to be treated biologically was investigated. The wastewater was originated from a factory producing a variety of pharmaceutical chemicals. Treatability studies were conducted under laboratory conditions with all chemicals (having COD varying from 900 to 7000 mg/L) produced in the factory in order to determine the operational conditions to utilize in the full-scale treatment plant. Optimum pH was determined as 3.5 and 7.0 for the first (oxidation) and second stage (coagulation) of the Fenton process, respectively. For all chemicals, COD removal efficiency was highest when the molar ratio of H(2)O(2)/Fe(2+) was 150-250. At H(2)O(2)/Fe(2+) ratio of 155, 0.3M H(2)O(2) and 0.002 M Fe(2+), provided 45-65% COD removal. The wastewater treatment plant that employs Fenton oxidation followed by aerobic degradation in sequencing batch reactors (SBR), built after these treatability studies provided an overall COD removal efficiency of 98%, and compliance with the discharge limits. The efficiency of the Fenton's oxidation was around 45-50% and the efficiency in the SBR system which has two reactors each having a volume of 8m(3) and operated with a total cycle time of 1 day, was around 98%, regarding the COD removal.

A study of the dental solid waste produced in a school of dentistry in Turkey.

Dental wastes are regulated under medical waste control regulations in most countries. Even though the quantity of hazardous wastes in dental solid wastes is a small proportion, there is still cross infection risk and potential danger for environment associated with mismanaged wastes. For this reason, knowledge of waste composition and development of proper management alternatives are necessary. In this study, the composition of solid wastes coming from eight clinics of the dental school of a University hospital in Turkey is examined. Although the waste has some variations between the two samplings, the general picture is such that the major components remain pretty much the same (in terms of %) for a fixed clinic. The composition of waste changes from one clinic to the other as expected. However, one can deduce from the data obtained that at about 35%, rubber gloves constitute close to the half of the total solid waste in almost all the clinics. Other major component is paper forming approximately 30% of the solid waste. In general, total waste coming from the clinics is related with the number of procedures conducted on patients at the clinics. Only a small fraction of the waste is hazardous indicating that at Hacettepe University School of Dentistry, hazardous waste collection rules are obeyed in most of the times.