Impact of Natural Organic Matter Competition on the Adsorptive Removal of Acetochlor and Metolachlor from Low-Specific UV Absorbance Surface Waters.

Although activated carbon adsorption is a very promising process for the removal of organic compounds from surface waters, the removal performance for nonionic pesticides could be adversely affected by co-occurring natural organic matter. Natural organic matter can compete with pesticides during the adsorption process, and the size of natural organic matter affects the removal of pesticides, as low-molecular-weight organics directly compete for adsorbent sites with pesticides. This study aims to investigate the competitive impact of low-molecular-weight organics on the adsorptive removal of acetochlor and metolachlor by four commercial powdered activated carbons. The adsorption features of selected powdered activated carbons were evaluated in surface water samples collected from the influent stream of the filtration process having 2.75 mg/L organic matter and 0.87 L/mg-m specific UV absorbance. The adsorption kinetics and capacities were examined by employing pseudo-first-order, pseudo-second-order, and intraparticle diffusion kinetic models and modified Freundlich and Langmuir isotherm models to the experimental data. The competitive removal of acetochlor and metolachlor in the presence of natural organic matter was evaluated for varied powdered activated carbon dosages on the basis of UV and specific UV absorbance values of adsorbed organic matter. The adsorption data were well represented by the modified Freundlich isotherm, as well as pseudo-second-order kinetics. The maximum organic matter adsorption capacities of the modified Freundlich isotherm were observed to be 120.6 and 127.2 mg/g by Norit SX Ultra and 99.5 and 100.6 mg/g by AC Puriss for acetochlor- and metolachlor-containing water samples, respectively. Among the four powdered activated carbons, Norit SX Ultra and AC Puriss provided the highest natural organic matter removal performances with 76 and 72% and 71 and 65% for acetochlor- and metolachlor-containing samples, respectively. Similarly, Norit SX Ultra and AC Puriss were very effective for adsorbing aromatic organics with higher than 80% specific UV absorbance removal efficiency. Metolachlor was almost completely removed by higher than 98% by Norit SX Ultra, Norit SX F Cat, and AC Puriss, even at low adsorbent dosages. However, an adsorbent dose of 100 mg/L and above should be added for all powdered activated carbons, except for Norit SX F Cat, for achieving an acetochlor removal performance of higher than 98%. The competition between low-molecular-weight organics (low-specific UV absorbance) and acetochlor and metolachlor was more apparent at low adsorbent dosages (10-75 mg/L).

Halogenated By-Products in Chlorinated Indoor Swimming Pools: A Long-Term Monitoring and Empirical Modeling Study.

Monitoring the disinfection process and swimming pool water quality is essential for the prevention of microbial infections and associated diseases. However, carcinogenic and chronic-toxic disinfection by-products (DBPs) are formed with reactions between disinfectants and organic/inorganic matters. DBP precursors in swimming pools originate from anthropogenic sources (body secretions, personal care products, pharmaceuticals, etc.) or chemicals used in pools. Temporal (48 weeks) water quality trends of trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), and halonitromethanes (HNMs) in two swimming pools (SP-A and SP-B) and precursor-DBP relationships were investigated in this study. Weekly samples were taken from swimming pools, and several physical/chemical water quality parameters, absorbable organic halides (AOX), and DBPs were determined. THMs and HAAs were the most detected DBP groups in pool water. While chloroform was determined to be the dominant THM compound, dichloroacetic acid and trichloroacetic acid were the dominant HAA compounds. The average AOX concentrations were measured to be 304 and 746 µg/L as Cl- in SP-A and SP-B, respectively. Although the amount of AOX from unknown chlorinated by-products in SP-A did not vary temporally, a significant increase in unknown DBP concentrations in SP-B was observed over time. AOX concentrations of chlorinated pool waters were determined to be an important parameter that can be used to estimate DBP concentrations.

Cyanophage-cyanobacterial interactions for sustainable aquatic environment.

Cyanobacteria are a type of bloom-forming phytoplankton that cause environmental problems in aquatic ecosystems worldwide. Cyanobacterial harmful algal blooms (cyanoHAB) often produce cyanotoxins that affect public health by contaminating surface waters and drinking water reservoirs. Conventional drinking water treatment plants are ineffective in treating cyanotoxins, even though some treatment methods are available. Therefore, innovative and advanced treatment methods are required to control cyanoHABs and their cyanotoxins. The goal of this review paper is to provide insight into the use of cyanophages as an effective form of biological control method for the removal of cyanoHABs in aquatic systems. Moreover, the review contains information on cyanobacterial blooms, cyanophage-cyanobacteria interactions, including infection mechanisms, as well as examples of different types of cyanobacteria and cyanophages. Moreover, the real-life application of cyanophages in marine and freshwater environments and the mode of action of cyanophages were compiled.

Removal of pesticides from secondary treated urban wastewater by reverse osmosis.

The residues of pesticides that reach water resources from agricultural activities in several ways contaminate drinking water resources and threaten aquatic life. This study aimed to investigate the performance of three reverse osmosis (RO) membranes (BW30-LE, SW30-XLE, and GE-AD) in rejecting four different pesticides (tributyl phosphate, flutriafol, dicofol, and irgarol) from secondary treated urban wastewater and also to elucidate the mechanisms underlying the rejection of these pesticides. RO experiments were conducted using pesticide-spiked wastewater samples under 10 and 20 bar transmembrane pressures (TMP) and membrane performances were evaluated. Overall, all the membranes tested exhibited over 95% rejection performances for all pesticides at both TMPs. The highest rejections for tributyl phosphate (99.0%) and irgarol (98.3%) were obtained with the BW30-LE membrane, while for flutriafol (99.9%) and dicofol (99.1%) with the GE-AD membrane. The increase in TMP from 10 to 20 bar did not significantly affect the rejections of all pesticides. The rejection performances of RO membranes were found to be governed by projection area as well as molecular weight and hydrophobicity/hydrophilicity of pesticides. Among the membranes tested, the SW30-XLE membrane was the most prone to fouling due to the higher roughness.

Modelling climate change impacts at a drinking water reservoir in Turkey and implications for reservoir management in semi-arid regions.

Climate change can have severe impacts on the water availability in semi-arid regions. In this study, we assessed the impact of climatic changes on water availability in the Altinapa Reservoir Watershed, located in the Konya province, south-central Turkey. Altinapa Reservoir supplies drinking water to Konya, a city of about 2 million population. We investigated possible changes in streamflow and reservoir storage over 2021-2098 under two representative concentration pathway scenarios (RCP4.5 and RCP8.5) developed based on GFDL-ESM2M, HadGEM2-ES, and MPI-ESM-MR global circulation models. We used a physically based model (SWAT-Soil and Water Assessment Tool) for understanding the hydrologic response of the basin to climatic changes. Results show that upward trends in air temperatures in the range of 0.01-0.04 °C/year and 0.005-0.06 °C/year are expected from 2021 to 2098 under the RCP4.5 and RCP8.5 scenarios, respectively. According to the HadGEM2-ES model, precipitation and streamflow would show a downward trend at a rate of 0.96 mm/year and 0.007 m3/s/year under the RCP4.5 scenario and at a rate of 1.62 mm/year and 0.01 m3/s/year under the RCP8.5 scenario, respectively. GFDL-ESM2M and MPI-ESM-MR models project upward trends in precipitation and streamflow under the RCP4.5 scenario (in the range of 0.64-1.28 mm/year and 0.0003-0.006 m3/s/year, respectively), and downward trends under the RCP8.5 scenario (in the range of 0.47-0.76 mm/year and 0.0015-0.003 m3/s/year, respectively). Reservoir storage is projected to increase slightly according to GFDL-ESM2M model and decrease according to the HadGEM2-ES, and MPI-ESM-MR models under both scenarios. Precipitation, streamflow, and reservoir storage predictions of GFDL-ESM2M and MPI-ESM-MR models are considerably lower than those observed in the basin in recent decades, showing that water resources will decrease in the future. The changes in water withdrawal patterns could cause further reductions in water availability. Good resilience to climate change can be achieved by a flexible water management system and by reducing water consumption and water losses in the watershed and from the reservoirs.

Selective removal of aluminum, nickel and chromium ions by polymeric resins and natural zeolite from anodic plating wastewater.

Aluminum industry has been well-known for producing enormous volume of wastewater in high concentration of varied heavy metals and toxic substances with wide variation in pH. In this study, selective removal of aluminum, nickel and chromium by polymeric resins (Amberlite IR120, Lewatit TP207) and natural zeolite from aluminum anodic plating process wastewater in varying aluminum concentrations (~10-200 mg/L), very low pH (3-4) and high conductivity (5090-8540 µS/cm) was evaluated. The wastewater was collected from a factory producing aluminum profiles (Kayseri, Turkey) where anodic oxidation plating is applied. The affinity of adsorbents towards to metals was in order aluminum > nickel > chromium. The kinetic results revealed that sorption of heavy metals onto adsorbent obeys pseudo-second-order model. The experimental data fitted the best to modified Freundlich isotherm. Aluminum uptake by adsorbents was feasible, exothermic and spontaneous by Amberlite IR120 and Lewatit TP207; however, the reaction was endothermic for zeolite.

Spatial/temporal distribution and multi-pathway cancer risk assessment of trihalomethanes in low TOC and high bromide groundwater.

This study aims (1) to determine the seasonal and spatial distribution of THMs formed in chlorinated groundwater containing low levels of organic matter (0.4-0.8 mg L-1) and low to high levels of bromine (40-380 µg L-1), and (2) to evaluate the multi-route cancer risks associated with them. The study was conducted in Kayseri (Turkey), where drinking water is supplied from groundwater after chlorination only. THM formation in 50 water samples from 18 storage tanks and 32 distribution points was investigated to evaluate the spatial and temporal changes in THM concentrations for 12 months. The lifetime cancer risk associated with exposure to THMs through multiple pathways (i.e., oral ingestion, dermal absorption, and inhalation) was estimated for males and females. For a 12 month sampling period, the minimum and maximum THM concentrations varied from 2 µg L-1 to 17 µg L-1 and from 2 µg L-1 to 29 µg L-1 in storage tanks and distribution points, respectively. The ranges of median concentrations of THM were 5 µg L-1 to 9 µg L-1 in storage tanks and 5 µg L-1 to 12 µg L-1 in distribution points. In all samples dibromochloromethane was the dominant species, followed by bromoform, chloroform, and bromodichloromethane. The average values of total cancer risk associated with exposure to THMs via oral ingestion, dermal absorption, and inhalation for females and males were 1.31 × 10-5 and 1.25 × 10-5 in storage tanks, and 1.46 × 10-5 and 1.39 × 10-5 in distribution points, respectively. Although THM concentrations were very low, cancer risk values are 1.0 × 10-6 < CR < 1.0 × 10-4, which are higher than the negligible risk level (1.0 × 10-6).

Sensitive Determination of Acetochlor, Alachlor, Metolachlor and Fenthion Utilizing Mechanical Shaking Assisted Dispersive Liquid-Liquid Microextraction Prior to Gas Chromatography-Mass Spectrometry.

A green, sensitive and accurate dispersive liquid-liquid microextraction (DLLME) method was used to preconcentrate four selected pesticides in dam lake water samples for determination by gas chromatography-mass spectrometry (GC-MS). Conditions of the DLLME method were comprehensively investigated and optimized according to type/volume of extraction solvent, type/volume of dispersive solvent, and type/period of mixing. The developed method was validated according to the limits of detection and quantitation, accuracy, precision and linearity. Under the optimum conditions, limit of detection values calculated for alachlor, acetochlor, metolachlor and fenthion were 1.7, 1.7, 0.2 and 7.8 µg/kg (mass based), respectively. The method recorded 202, 104, 275 and 165 folds improvement in detection power values for acetochlor, alachlor, metolachlor and fenthion, respectively, when compared with direct GC-MS measurements. In order to evaluate the accuracy of the developed method, real sample application with spiking experiments was performed on dam lake water samples, and satisfactory percent recovery results in the range of 81%-120% were obtained.

Removal of heavy metals from aluminum anodic oxidation wastewaters by membrane filtration.

Aluminum manufacturing has been reported as one of the largest industries and wastewater produced from the aluminum industry may cause significant environmental problems due to variable pH, high heavy metal concentration, conductivity, and organic load. The management of this wastewater with a high pollution load is of great importance for practitioners in the aluminum sector. There are hardly any studies available on membrane treatment of wastewater originated from anodic oxidation. The aim of this study is to evaluate the best treatment and reuse alternative for aluminum industry wastewater using membrane filtration. Additionally, the performance of chemical precipitation, which is the existing treatment used in the aluminum facility, was also compared with membrane filtration. Wastewater originated from anodic oxidation coating process of an aluminum profile manufacturing facility in Kayseri (Turkey) was used in the experiments. The characterization of raw wastewater was in very low pH (e.g., 3) with high aluminum concentration and conductivity values. Membrane experiments were carried out with ultrafiltration (PTUF), nanofiltration (NF270), and reverse osmosis (SW30) membranes with MWCO 5000, 200-400, and 100 Da, respectively. For the chemical precipitation experiments, FeCl3 and FeSO4 chemicals presented lower removal performances for aluminum and chromium, which were below 35% at ambient wastewater pH ~ 3. The membrane filtration experimental results show that, both NF and RO membranes tested could effectively remove aluminum, total chromium and nickel (>90%) from the aluminum production wastewater. The RO (SW30) membrane showed a slightly higher performance at 20 bar operating pressure in terms of conductivity removal values (90%) than the NF 270 membrane (87%). Although similar removal performances were observed for heavy metals and conductivity by NF270 and SW30, significantly higher fluxes were obtained in NF270 membrane filtration at any pressure that there were more than three times the flux values in SW30 membrane filtration. Due to the lower heavy metal (<65%) and conductivity (<30%) removal performances of UF membrane, it could be evaluated as pretreatment followed by NF filtration to protect and extend NF membrane life. The water treated by both NF and RO could be recycled back into the process to be reused with economic and environmental benefits.

Impact of combining chlorine dioxide and chlorine on DBP formation in simulated indoor swimming pools.

The main objective of this study was to assess the combined use of chlorine dioxide (ClO2) and chlorine (Cl2) on the speciation and kinetics of disinfection by-product (DBP) formation in swimming pools using synthetic pool waters prepared with a body fluid analog (BFA) and/or fresh natural water. At 1:25 (mass ratio) of ClO2 to Cl2, there was no significant reduction in the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) for both BFA solution and natural water compared to the application of Cl2 alone. When the mass ratio of ClO2 to Cl2 increased to 1:1, substantial decreases in both THMs and HAAs were observed in the natural water, while there was almost no change of DBP formations in the BFA solution. Haloacetonitriles and halonitromethanes levels in both water matrices remained similar. In the presence of bromide, the overall DBP formation increased in both BFA solution and natural water. For the DBP formation kinetics, after 72hr of contact time, very low formation of THMs and HAAs was observed for the use of ClO2 only. Compared to Cl2 control, however, applying the 1:1 mixture of ClO2/Cl2 reduced THMs by >60% and HAAs by >50%. Chlorite was maintained below 1.0mg/L, while the formation of chlorate significantly increased over the reaction time. Finally, in a bench-scale indoor pool experiment, applying ClO2 and Cl2 simultaneously produced less THMs compared to Cl2 control and kept chlorite at <0.4mg/L, while HAAs and chlorate accumulated over 4-week operation period.

The roles of tertiary amine structure, background organic matter and chloramine species on NDMA formation.

N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated and chlorinated drinking waters and wastewaters. Formation mechanisms and precursors of NDMA are still not well understood. The main objectives of this study were to systematically investigate (i) the effect of tertiary amine structure, (ii) the effect of background natural organic matter (NOM), and (iii) the roles of mono vs. dichloramine species on the NDMA formation. Dimethylamine (DMA) and 20 different tertiary aliphatic and aromatic amines were carefully examined based on their functional groups attached to the basic DMA structure. The wide range (0.02-83.9%) of observed NDMA yields indicated the importance of the structure of tertiary amines, and both stability and electron distribution of the leaving group of tertiary amines on NDMA formation. DMA associated with branched alkyl groups or benzyl like structures having only one carbon between the ring and DMA structure consistently gave higher NDMA yields. Compounds with electron withdrawing groups (EWG) reacted preferentially with monochloramine, whereas compounds with electron donating group (EDG) showed tendency to react with dichloramine to form NDMA. When the selected amines were present in NOM solutions, NDMA formation increased for compounds with EWG while decreased for compounds with EDG. This impact was attributed to the competitions between NOM and amines for chloramine species. The results provided additional information to the commonly accepted mechanism for NDMA formation including chloramine species reacting with tertiary amines and the role of the leaving group on overall NDMA conversion.

Formation of chlorination by-products in waters with low SUVA--correlations with SUVA and differential UV spectroscopy.

The formation of THMs and HAAs after chlorination of bulk water fractions of low-SUVA (specific UV absorbance) surface waters was investigated, and the applicability of SUVA and differential UV spectroscopy for monitoring THMs and HAAs in such waters was evaluated. Samples from two reservoirs were fractionated employing XAD-8, XAD-4, MIEX resin and granular activated carbon adsorption. A total of 83 bulk water NOM fractions (i.e., the remaining solutions after contact with the adsorbent or resin at various doses) were obtained and chlorinated. The majority of NOM in both waters was found to have average molecular weights <2000 Da and SUVA values <2L/mg Cm, indicating that NOM in the tested waters contained dominantly lower molecular weight fractions and low aromaticity. SUVA did not correlate well with the formation and speciation of THMs and HAAs, suggesting that SUVA does not capture the reactive sites on NOM moieties responsible for DBP formation in low-SUVA waters. Similarly, no correlations were found among THMs/HAAs formations and differential UV spectroscopy, indicating the formation of DBPs independent of destruction in UV-absorbing sites. In all fractions, concentrations of THMs were higher than those of HAAs. Chlorinated DBP species were dominant over brominated ones due to low bromide concentrations. The results overall suggested that low- or non-UV-absorbing NOM moieties play important roles in the formation of DBPs in waters with low SUVA, low DOC and low bromide levels.

Occurrence of disinfection by-products in low DOC surface waters in Turkey.

A total of 29 surface waters from different regions of Turkey were sampled once a month during 2004. Filtered raw water samples were characterized, chlorinated and the concentrations of disinfection by-products (DBPs) were measured. All waters were low in DOC ranging from 0.91 to 4.42 mg/L. The range of annual average trihalomethanes (THMs) and haloacetic acids (HAAs) concentrations in all waters was 21-189 and 18-149mug/L, respectively. Total mass contributions of halides in THMs and HAAs to absorbable organic halides (AOX) ranged between 10 and 56% in all waters on annual average basis, indicating that significant amounts of other DBPs are being formed in the majority of the tested waters. A strong linear correlation was obtained between the concentrations of THMs and HAAs. Rather poor correlations were found for THMs-AOX and HAAs-AOX levels. For both THMs and HAAs, chlorinated species dominated over brominated ones since the majority of water sources had very low bromide levels. While chloroform and trichloroacetic acid were the major THM and HAA compounds, respectively; the extent of formation and speciation of DBPs varied greatly by season and water source. No consistent general trends were observed in terms of seasonal variations in DBP levels, suggesting that the characteristics of NOM moieties and their chlorine reactivity vary by season in almost all waters tested.