RESUMO
Activated carbon adsorption is an effective method for removing perfluoroalkyl substances (PFAS) from water. However, the observation that higher concentrations of PFAS are observed after treatment than before (i.e., desorption) is an important, unsolved issue. In this study, to elucidate PFAS desorption and its relationship with PFAS properties, we conducted solvent extraction and long-term desorption experiments using granular activated carbon (GAC) that had been loaded with PFAS in two actual drinking water treatment plants. The amount of PFAS extracted from GAC depended on the depth in the GAC filter; longer-chain and hydrophobic PFAS were present in relatively higher amounts in the shallow part compared to the deep part of the GAC filter, whereas shorter-chain and hydrophilic PFAS were present in relatively higher amounts in the deep part compared to the shallow part. This pattern was probably due to a chromatographic effect by which hydrophilic PFAS adsorbed once, subsequently desorbed, and migrated from the shallow part of the GAC filter to the deeper part. The desorption potential of PFAS to water (i.e., the maximum amount of PFAS desorbed to water per unit mass of GAC) was estimated by conducting long-term bottle-point desorption tests and analyzing the relationship between the equilibrium water-phase concentration of PFAS in a bottle containing GAC and the amount of PFAS desorbed to water per unit GAC mass. The desorption ratio (ratio of desorption potential to loading) was the highest for PFAS for which the logarithm of the octanol/water distribution coefficient (Log DOW) ranged from -1 to 1. The implication was that most of those PFAS removed by GAC were likely to return to the water as the external water-phase concentrations dropped. The decrease of the desorption ratio to 20 % as Log DOW increased suggested irreversible adsorption due to hydrophobic affinity.
Assuntos
Água Potável , Fluorocarbonos , Poluentes Químicos da Água , Purificação da Água , Carvão Vegetal/química , Água Potável/análise , Poluentes Químicos da Água/análise , Fluorocarbonos/análise , Purificação da Água/métodos , AdsorçãoRESUMO
Granular or powdered activated carbon (GAC/PAC) processes are installed in full-scale drinking water treatment plants (DWTPs) to reduce disinfection byproduct precursors, odor, ammonia, and pesticides. This study investigated the ability of GAC/PAC processes in 23 DWTPs to remove per- and polyfluoroalkyl substances (PFASs). In the GAC process, filter breakthrough of perfluoroalkyl carboxylic acids (PFCAs) occurred faster as the PFCA chain length is decreased. During periods of high water temperatures (20-29 °C), the effluent concentration of two short-chain PFCAs (C4 and C5) surpassed that of the influent after the throughput reached 5,000-7,500 bed volumes (equivalent to 2-3 months) due to desorption. However, such desorption was not observed during periods of low water temperatures (5-19 °C). Meanwhile, long-chain PFCAs were consistently removed, as the GAC was replaced before breakthrough became noticeable. PFAS removal deteriorated at a remarkably fast rate after a partial breakthrough of several tens of percent. Biological activated carbon was proved ineffective in removing PFASs due to its diminished adsorption capacity after long-term use. The PAC process, however, exhibited a slight decrease in PFCA residual (10%) at higher water temperatures (15-30 °C). The PAC dose required for a certain residual ratio was lower with an increase in the hydrophobicity of PFAS; C8-PFCA only required 20 mg/L of PAC for 50% removal, while C4-PFCA required a significantly higher dose of 100-700 mg/L. Consequently, the activated carbon process, which removes organic contaminants in surface water, was inadequate in removing PFASs, particularly those with short chains. Thus, it is recommended that GAC filters be replaced more frequently (within two months) for short-chain PFAS removal. Further, the adsorption performance of PAC must be enhanced.
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Application of poly-aluminum chloride (PACl) coagulant is a popular mode of water treatment worldwide because of the high capacity of PACl to neutralize charge. The manufacture and use of PACls with various basicities in different regions around the world suggest that the characteristics of the raw water are important determinants of the efficacy of PACl application. However, attention has not been fully paid to the effects of water quality other than the substances to be removed. In this study, two typical PACls with different basicities were used to investigate why the performance of PACls depends on the characteristics of the raw water. We focused on the concentrations of inorganic ions in the raw water. Use of high-basicity PACl (HB-PACl) with a high content of polymeric-colloidal species (Alb+Alc) resulted in very slow floc formation and little turbidity removal in raw water with low concentrations of sulfate ions. The performance of the HB-PACl was inferior to that of normal-basicity PACl (NB-PACl), although the charge-neutralization capacity of the HB-PACl was higher. Rates of floc formation were strongly correlated with the rate of aluminum precipitation by hydrolysis reaction, which was identified as an indicator for evaluating the compatibility of raw water with PACl treatment. Among the common ions in natural water, the sulfate ion had the greatest ability to hydrolyze and precipitate PACl because of its divalency and tetrahedral structure. This conclusion followed from experimental results showing similar effects for selenate and chromate ions as for sulfate ions and somewhat smaller effects for thiosulfate ions. Bicarbonate ions and natural organic matter affected PACl hydrolysis-precipitation, but chloride ions, nitrate ions, and cations had little effect on PACl hydrolysis-precipitation. Interestingly, the abilities of sulfate ions to hydrolyze HB-PACl and NB-PACl were very similar, but bicarbonate ions were less effective in hydrolyzing HB-PACl than NB-PACl, and bicarbonate ions contributed little to the hydrolysis-precipitation of HB-PACl in raw water with normal alkalinity. Therefore, sufficient coagulation with HB-PACl therefore usually requires a certain concentration of sulfate ions in water to be treated. The implication is that which anions are most influential to the hydrolysis-precipitation of PACl, and thus to PACl's coagulation ability depends on the constituents of the PACl.
Assuntos
Cloretos , Purificação da Água , Bicarbonatos , Hidróxido de Alumínio/química , Alumínio/química , Sulfatos/química , Purificação da Água/métodos , FloculaçãoRESUMO
Proper selection of new contaminants to be regulated or monitored prior to implementation is an important issue for regulators and water supply utilities. Herein, we constructed and evaluated machine learning models for predicting the detectability (detection/non-detection) of pesticides in surface water as drinking water sources. Classification and regression models were constructed for Random Forest, XGBoost, and LightGBM, respectively; of these, the LightGBM classification model had the highest prediction accuracy. Furthermore, its prediction performance was superior in all aspects of Recall, Precision, and F-measure compared to the detectability index method, which is based on runoff models from previous studies. Regardless of the type of machine learning model, the number of annual measurements, sales quantity of pesticide for rice-paddy field, and water quality guideline values were the most important model features (explanatory variables). Analysis of the impact of the features suggested the presence of a threshold (or range), above which the detectability increased. In addition, if a feature (e.g., quantity of pesticide sales) acted to increase the likelihood of detection beyond a threshold value, other features also synergistically affected detectability. Proportion of false positives and negatives varied depending on the features used. The superiority of the machine learning models is their ability to represent nonlinear and complex relationships between features and pesticide detectability that cannot be represented by existing risk scoring methods.
Assuntos
Água Potável , Praguicidas , Poluentes Químicos da Água , Praguicidas/análise , Qualidade da Água , Água Potável/análise , Monitoramento Ambiental , Poluentes Químicos da Água/análise , Aprendizado de MáquinaRESUMO
Catalytic oxidative removal of Mn2+ on activated-carbon surfaces by free chlorine was recently discovered and found to be potentially practicable for water treatment when using micrometer-sized activated carbon. Herein, we newly derived a kinetic model for trace-substance removal by catalytic reaction and applied it to the Mn2+ removal. External-film mass transfer, adsorption, and oxidation/desorption contributed similarly to the Mn2+ removal rate under actual practical conditions. The low removal rate in natural water was attributed to decreases in available adsorption sites: e.g., a 50% decrease in available sites in water with 0.26 mmol-Ca2+/L caused a 15% reduction in removal rate. Low temperature greatly reduced the removal rate by both enhancing the decrease in available sites and hindering mass transfer through increased viscosity. While adsorption sites differed 8-fold between different carbon particles, causing a 2.2-fold difference in removal rates, carbon particle size was more influential, with a >10-fold difference between 2- and 30-µm sizes.
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Submerged-membrane hybrid systems (SMHSs) that combine membrane filtration with powdered activated carbon (PAC) take advantage of PAC's ability to adsorb and remove contaminants dissolved in water. However, the risk of contaminant desorption due to temporal changes in the influent concentration of the contaminant has not been thoroughly explored. In this study, we used a SMHS with conventionally-sized PAC or superfine PAC (SPAC) to remove 2-methylisoborneol (MIB), a representative micropollutant, from water containing natural organic matter (NOM), with the goal of elucidating adsorption-desorption phenomena in the SMHS. We found that 20-40% of the MIB that adsorbed on PAC and SPAC while the influent was contaminated with MIB (6 h, contamination period) desorbed to the liquid phase within 6 h from the time that the MIB-containing influent was replaced by MIB-free influent (no-contamination period). The percentage of desorption during the no-contamination period increased with increasing MIB breakthrough concentration during the contamination period. These findings indicate that the PAC/SPAC in the SMHS should be replaced while the breakthrough concentration is low, not only to keep a high removal rate but also to decrease the desorption risk. SPAC is fast in removal by adsorption, but it is also fast in release by desorption. SPAC (median diameter: 0.94 µm) showed almost the same adsorption-desorption kinetics as PAC (12.1 µm) of a double dose. A two-component branched-pore diffusion model combined with an IAST (ideal adsorbed solution theory)-Freundlich isotherm was used to describe and analyze the adsorption-desorption of MIB. The diffusivity of MIB molecules in the pores of the activated carbon particles decreased markedly in a short period of time. This decrease, which was attributed to fouling of the activated carbon in the SMHS by coagulant-treated water containing NOM, not only reduced the rate of MIB removal during the contamination period but also hindered the rate of MIB desorption during the no-contamination period and thus prevented the effluent MIB concentration from becoming high. On the other hand, coagulation did not change the concentration of NOM that competes with MIB for adsorption sites.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Adsorção , Carvão Vegetal , Cinética , Pós , Poluentes Químicos da Água/análiseRESUMO
The discharged state affects the charge transfer resistance of lithium-ion secondary batteries (LIBs), which is referred to as the depth of discharge (DOD). To understand the intrinsic charge/discharge property of LIBs, the DOD-dependent charge transfer resistance at the solid-liquid interface is required. However, in a general composite electrode, the conductive additive and organic polymeric binder are unevenly distributed, resulting in a complicated electron conduction/ion conduction path. As a result, estimating the DOD-dependent rate-determining factor of LIBs is difficult. In contrast, in micro/nanoscale electrochemical measurements, the primary or secondary particle is evaluated without using a conductive additive and providing an ideal mass transport condition. To control the DOD state of a single LiFePO4 active material and evaluate the DOD-dependent charge transfer kinetic parameters, we use scanning electrochemical cell microscopy (SECCM), which uses a micropipette to form an electrochemical cell on a sample surface. The difference in charge transfer resistance at the solid-liquid interface depending on the DOD state and electrolyte solution could be confirmed using SECCM.
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One of the main purposes of drinking water treatment is to reduce turbidity originating from clay particles. Relatively little is known about the removal of other types of particles, including conventionally sized powdered activated carbon (PAC) and superfine PAC (SPAC), which are intentionally added during the treatment process; microplastic particles; and viruses. To address this knowledge gap, we conducted a preliminary investigation in full-scale water treatment plants and then studied the removal of these particles during coagulation-flocculation, sedimentation, and rapid sand filtration (CSF) in bench-scale experiments in which these particles were present together. Numbers of all target particles were greatly decreased by coagulation-flocculation and sedimentation (CS). Subsequent rapid sand filtration greatly reduced the concentrations of PAC and SPAC but not the concentrations of viruses, microplastic particles, and clay particles. Overall removal rates by CSF were 4.6 logs for PAC and SPAC, 3.5 logs for viruses, 2.9 logs for microplastics, and 2.8 logs for clay. The differences in removals were not explained by particle sizes or zeta potentials. However, for clays, PAC and SPAC, for which the particle size distributions were wide, smaller particles were less efficiently removed. The ratios of both clay to PAC and clay to SPAC particles increased greatly after rapid sand filtration because removal rates of PAC and SPAC particles were about 2 logs higher than removal rates of clay particles. The trend of greater reduction of PAC concentrations than turbidity was confirmed by measurements made in 14 full-scale water purification plants in which residual concentrations of PAC in treated water were very low, 40-200 particles/mL. Clay particles therefore accounted for most of the turbidity in sand filtrate, even though PAC was employed. The removal rate of microplastic particles was comparable to that of clays. Sufficient turbidity removal would therefore provide comparable removal of microplastics. We investigated the effect of mechanical/photochemical weathering on the removal of microplastics via CSF. Photochemical weathering caused a small increment in the removal rate of microplastics during CS but a small reduction in the removal rate of microplastics during rapid sand filtration; mechanical weathering decreased the removal rate via CS but increased the removal rate via rapid sand filtration. The changes of removal of microplastics might have been caused by changes of their zeta potential.
Assuntos
Vírus , Purificação da Água , Bentonita , Carvão Vegetal , Argila , Filtração , Floculação , Caulim , Microplásticos , Plásticos , AreiaRESUMO
Drinking water quality guideline values for toxic compounds are determined based on their acceptable daily intake. The toxicological end point for determining the acceptable daily intake of most organophosphorus insecticides is inhibition of acetylcholinesterase (AChE). Although insecticides ingested with drinking water are partly metabolized by the liver before transport to the rest of the body, no current cell-independent AChE activity assay takes the effects of metabolism into account. Here, we incorporated metabolism into a cell-independent AChE activity assay and then evaluated the change in anti-AChE activity during chlorination of a solution containing the organophosphorus insecticide diazinon. The anti-AChE activities of solutions of diazinon or diazinon-oxon, the major transformation product of diazinon during chlorination, were dramatically changed by metabolism: the activity of diazinon solution was markedly increased, whereas that of diazinon-oxon solution was slightly decreased, clearly indicating the importance of incorporating metabolism into assays examining toxicity after oral ingestion. Upon chlorination, diazinon was completely transformed, in part to diazinon-oxon. Although diazinon solution without metabolism did not show anti-AChE activity before chlorination, it did after chlorination. In contrast, with metabolism, diazinon solution did show anti-AChE activity before chlorination, but chlorination gradually decreased this activity over time. The observed anti-AChE activities were attributable solely to diazinon and diazinon-oxon having been contained in the samples before metabolism, clearly suggesting that the presence not only of diazinon but also of diazinon-oxon should be monitored in drinking water. Further examination using a combination of tandem mass spectrometry and in silico site-of-metabolism analyses revealed the structure of a single metabolite that was responsible for the observed anti-AChE activity after metabolism. However, because this compound is produced via metabolism in the human body after oral ingestion of diazinon, its presence in drinking water need not be monitored and regulated.
Assuntos
Acetilcolinesterase/metabolismo , Inibidores da Colinesterase/toxicidade , Diazinon/toxicidade , Inseticidas/toxicidade , Inibidores da Colinesterase/química , Inibidores da Colinesterase/metabolismo , Simulação por Computador , Diazinon/química , Diazinon/metabolismo , Ensaios Enzimáticos , Halogenação , Humanos , Inseticidas/química , Inseticidas/metabolismo , Internet , Compostos Organofosforados/química , Compostos Organofosforados/metabolismo , Compostos Organofosforados/toxicidadeRESUMO
1,4-Dioxane is one of the most persistent organic micropollutants in conventional drinking-water-treatment processes. Vacuum ultraviolet (VUV) treatment is a promising means of removing micropollutants such as 1,4-dioxane from source water, but this approach has not yet been implemented in a full-scale water treatment plant, partly because the operating parameters for pilot and full-scale VUV photoreactors have not been optimized. Here, we developed a computational fluid dynamics-based method for optimizing VUV photoreactor performance through energy-based analyses that take into account the effects of two important operating parameters-flow rate and radiant exitance. First, we constructed a computational fluid dynamics model and determined the sole parameter required for the model, the pseudo-first-order rate constant for the reaction of 1,4-dioxane, by simple batch experiment. Then, we validated the model by using a pilot-scale flow-through annular photoreactor. Finally, we used the validated model to examine the effects of flow rate and radiant exitance on the efficiency of 1,4-dioxane degradation in a virtual annular photoreactor. Radiation efficiency, which was defined as the ratio of the logarithmic residual ratio of 1,4-dioxane to the theoretical minimum logarithmic residual ratio (best possible performance) under the given operating conditions, was calculated as an energy-based index of cost-effectiveness. Radiation efficiency was found to increase with increasing flow rate but decreasing radiant exitance. An electrical energy per order (EEO) analysis suggested that VUV treatment under laminar flow was most economical when low-power lamps and a high flow rate were used. In contrast, VUV treatment under turbulent flow was suggested to be most economical when high-power lamps were used at a high flow rate.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Dioxanos , Hidrodinâmica , Oxirredução , Raios Ultravioleta , VácuoRESUMO
The elution of lead, and nickel from water supply devices into water is a potential health concern. This study was performed to examine the actual concentrations of nickel and lead in the water from taps in homes and offices, focusing on the differences between first flush and fully flushed water. The water quality management target value and water quality standard in Japan specify nickel and lead concentrations in drinking water <20 and <10 µg/L, respectively. Nickel concentration in the first flush water (100 mL) from 110 household taps revealed 22 cases (20%) > 20 µg/L, while the fully flushed water satisfied the standard after running 5000 mL of water. The nickel concentration decreased gradually in sequential sampling of each 100 mL from the taps. Lead concentration in the first flush water exceeded the standard in 32 cases (29%), while the fully flushed water was below the target value. The concentration in the first flush water tended to decrease with time since the tap installation, and this was significant after 10 years for nickel but not significant for lead. It is important to flush retained water out of the tap after several hours without use. No significant correlation was found with the volume of the test faucet in the market, but bronze-based products showed higher nickel concentrations than brass and plastic products.
Assuntos
Água Potável , Poluentes Químicos da Água , Água Potável/análise , Japão , Chumbo/análise , Níquel , Poluentes Químicos da Água/análise , Abastecimento de ÁguaRESUMO
Although superfine powdered activated carbon has excellent adsorption properties, it is not used in conventional water treatment processes comprising coagulation-flocculation, sedimentation, and sand filtration (CSF) due to concerns about its residual in treated water. Here, we examined the production and fate of very fine carbon particles with lacking in charge neutralization as a source of the residual in sand filtrate after CSF treatment. Almost all of the carbon particles in the water were charge-neutralized by coagulation treatment with rapid mixing, but a very small amount (≤0.4% of the initial concentration) of very fine carbon particles with a lesser degree of charge neutralization were left behind in coagulation process. Such carbon particles, defined as stray carbon particles, were hardly removed by subsequent flocculation and sedimentation processes, and some of them remained in the sand filtrate. The concentration of residual carbon particles in the sand filtrate varied similarly with that of the stray carbon particles. The stray and residual carbon particles were similarly smaller than the particles before coagulation treatment, but the residual carbon particles had less charge neutralization than the stray carbon particles. The turbidity of water samples collected after sedimentation was not correlated with the residual carbon concentration in the sand filtrate, even though it is often used as an indicator of treatment performance with respect to the removal of suspended matter. Based on these findings, we suggest that reduction of the amount of stray particles should be a performance goal of the CSF treatment. Examining this concept further, we confirmed that the residence time distributions in the coagulation and flocculation reactors influenced the concentration of stray carbon particles and then the residual carbon particle concentration in sand filtrate, but found that the effect was dependent on coagulant type. A multi-chambered-reactor configuration lowered both the stray carbon particle concentration after coagulation treatment and the residual carbon particle concentration in sand filtrate compared with a single-chambered reactor configuration. When a normal basicity PACl that consisted mainly of monomeric Al species was used, the stray carbon particle concentration was decreased during coagulation process and then gradually decreased during subsequent flocculation process because the monomeric Al species were transformed to colloidal Al species via polymeric Al species. In contrast, when a high-basicity PACl that consisted mostly of colloidal Al species was used, coagulation treatment largely decreased the stray carbon particle concentration, which did not decrease further during subsequent flocculation process. These findings will be valuable for controlling residual carbon particles after the CSF treatment.
Assuntos
Carvão Vegetal , Purificação da Água , Floculação , Pós , AreiaRESUMO
Several risk scoring and ranking methods have been applied for the prioritization of micropollutants, including pesticides, and in the selection of pesticides to be regulated regionally and nationally. However, the effectiveness of these methods has not been evaluated in Japan. We developed a risk prediction method to select pesticides that have a high probability of being detected in drinking water sources where no monitoring data is available. The risk prediction method was used to select new pesticides for the 2013 Primary List in the Japanese Drinking Water Quality Guidelines. Here, we examined the effectiveness of the method on the basis of the results of water quality examinations conducted by water supply authorities across Japan, and studied ways to improve the risk prediction method. Of the 120 pesticides in the 2013 Primary List, 80 were detected in drinking water sources (raw water entering water treatment plants). The rates of detection of the newly selected pesticides and previously listed pesticides were not significantly different: 64% and 68%, respectively. When the risk predictor was revised to incorporate degradability of dry-field pesticides and current pesticide sales data, the rate of detection of pesticides selected as having a high risk of detection improved from 72% to 88%. We prepared regional versions of the Primary List using the revised risk predictors and verified their utility. The number of listed pesticides varied greatly by region, ranging from 32 to 73; all regional lists were much shorter than the national Primary List. In addition, 55% to 100% of the pesticides detected in each region were included in a Regional Primary List. This work verifies the ability of the risk prediction method to screen pesticides and select those with a high risk of detection.
Assuntos
Água Potável , Praguicidas , Poluentes Químicos da Água , Monitoramento Ambiental , Japão , Praguicidas/análise , Poluentes Químicos da Água/análise , Qualidade da ÁguaRESUMO
Here, we examined the removal of soluble divalent manganese (Mn(II)) by combination treatment with superfine powdered activated carbon (SPAC) and free chlorine in a membrane filtration pilot plant and batch experiments. Removal rates >95% were obtained with 3 mg/L SPAC, 1 mg/L chlorine, and a contact time of 4 min, meeting practical performance standards. Mn(II) was found to be oxidized and precipitated on the surface of the activated carbon particles by chlorine. The Mn(II) removal rate was fitted to pseudo-first-order reaction kinetics, and the rate coefficient changed in inverse proportion to as-is particle size, but not to true particle size. The rate coefficient was independent of both Mn(II) concentration, except at high Mn(II) concentration, and the chlorine concentrations tested. The rate-determining step of Mn(II) removal was confirmed to be external-film mass transfer, not chemical oxidation. Activated carbon was found to have a catalytic effect on the oxidation of Mn(II), but the effect was minimal for conventionally sized activated carbon. However, Mn(II) removal at feasible rates for practical application can be expected when the activated carbon particle diameter is reduced to several micrometers. Activated carbon with a particle size of around 1-2 µm may be the most appropriate for Mn(II) removal because particles below this size were aggregated, resulting in reduced removal efficiency.
Assuntos
Carvão Vegetal , Purificação da Água , Adsorção , Cloro , Manganês , Estresse Oxidativo , PósRESUMO
Vacuum ultraviolet (VUV) treatment is a promising advanced oxidation process for the removal of organic contaminants during water treatment. Here, we investigated the formation of disinfection by-products from coexisting organic matter during VUV or ultraviolet (UV) treatment following pre-chlorination, and their fates after post-chlorination, in a standard Suwannee River humic acid water and a natural lake water. VUV treatment after pre-chlorination decreased the total trihalomethane (THM) concentration but increased total aldehyde and chloral hydrate concentrations; total haloacetic acid (HAA) and haloacetonitrile (HAN) concentrations did not change. UV treatment after pre-chlorination produced similar changes in the by-products as those observed for VUV treatment, with the exception that the total THM concentration was not changed, and the total HAN concentration was increased. The final concentrations of by-products after post-chlorination were increased by VUV or UV treatment, except for the total HAA concentration, which remained unchanged after UV treatment. The increases were greater after VUV treatment than after UV treatment, probably because the larger amount of hydroxyl radicals generated during VUV treatment compared with during UV treatment transformed coexisting organic matter into precursors of by-products that were then converted to by-products during post-chlorination.
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Organophosphorus insecticides are known to be partly transformed to their respective oxons during the chlorination step of drinking water treatment. For most organophosphorus insecticides, the toxicological endpoint for determining acceptable daily intake levels is inhibition of acetylcholinesterase (AChE). Like the parent insecticides, oxons also inhibit AChE, so the presence of oxons in drinking water is also evaluated. However, no attention is paid to the possible presence of transformation products (TPs) other than oxons. In the present study, we determined whether the anti-AChE activity observed for chlorinated solutions of the organophosphorus insecticides malathion and methidathion could be solely attributed to the parent compounds and their oxons. Upon chlorination, both malathion and methidathion were immediately transformed to their oxons; the maximum transformation ratios were 60% and 30%, respectively, indicating that at least 40% and 70% of these compounds were transformed into other TPs. Before chlorination, malathion- and methidathion-containing solutions exhibited little to no anti-AChE activity, but the solutions showed strong activity after chlorination. The contributions of the parent insecticides and their oxons to the activities of the chlorinated samples were calculated from the concentrations of the compounds in the samples and dose-response curves for chemical standards of the compounds. For both the malathion-containing solution and the methidathion-containing solution, the calculated anti-AChE activities were almost the same as the observed activities at every chlorination time. This suggests that the observed activities could be attributed solely to the parent insecticides and their oxons, indicating that other TPs need not be considered.
Assuntos
Halogenação , Inseticidas/química , Compostos Organofosforados/química , Acetilcolinesterase , Animais , Inibidores da Colinesterase/química , Inseticidas/farmacologia , Malation/química , Compostos Organotiofosforados/química , Purificação da Água/métodosRESUMO
Although agricultural activities-especially paddy rice cultivation-are prominent in watersheds in Asian countries, few comprehensive studies have examined pesticide concentrations in water in these areas. Here, we report the concentrations of 162 pesticides in treated drinking water and source water (14,076 samples) in Japan, where rice cultivation is common, along with trends in sales of herbicides, fungicides, and insecticides from 1963 to 2016. Herbicides and fungicides-especially those used in rice farming were frequently detected in drinking water sources. The herbicide bromobutide, which is not listed in drinking water quality standards or guidelines except in Japan, as well as the widely used-and-detected bentazone, were frequently detected in source water (bromobutide and bentazone were detected at concentrations >0.1 µg/L in 31.1% and 33.8% of samples, respectively). Dymron and tefuryltrione were also detected in over 10% of samples at concentrations >0.1 µg/L. The highest observed concentration of bromobutide was 10 µg/L, and 7.5% of samples had concentrations >1 µg/L. High concentrations were also observed for halosulfuron methyl (7.9 µg/L), pyroquilon (7.0), molinate (6.8), and metominostrobin (4.6). Some of the pesticides frequently detected in source water were not detected at all in drinking water, but the main cause of the non-detection appeared to be degradation by chlorine. From the 1970s onward, sales of herbicides and fungicides with higher acceptable daily intakes (ADIs; i.e., with lower toxicity) have increased. However, the percentage of herbicides with very low ADIs (<10-2.5 mg kg-1 d-1) being shipped has also increased. Tefuryltrione, which was detected at normalized concentrations >0.1 in 8% of samples, is an example of this type of herbicide. The average log-Kow of herbicides has decreased from the 1970s to the present, due to the strong trend towards the application of hydrophilic herbicides, such glyphosate. The need for increased monitoring of pesticides used in rice paddy farming is highlighted.
Assuntos
Água Potável , Herbicidas/análise , Praguicidas/análise , Poluentes Químicos da Água/análise , Agricultura , Ásia , Monitoramento Ambiental , JapãoRESUMO
Many PACl (poly-aluminum chloride) coagulants with different characteristics have been trial-produced in laboratories and commercially produced, but the selection of a proper PACl still requires empirical information and field testing. Even PACls with the same property sometimes show different coagulation performances. In this study, we compared PACls produced by AlCl3-titration and Al(OH)3-dissolution on their performance during coagulation-flocculation, sedimentation, and sand filtration (CSF) processes. The removal targets were particles of superfine powdered activated carbon (SPAC), which are used for efficient adsorptive removal of micropollutants, but strict removal of SPAC is required because of the high risk of their leakage after CSF. PACls of high-basicity produced by AlCl3-titration and Al(OH)3-dissolution were the same in terms of the ferron assay and colloid charge, but their performance in CSF were completely different. High-basicity Al(OH)3-dissolution PACls formed large floc particles and yielded very few remaining SPAC particles in the filtrate, whereas high-basicity AlCl3-titration PACls did not form large floc particles. High-basicity PACls produced by Al(OH)3-dissolution were superior to low-basicity PACl in lowering remaining SPAC particles by the same method because of their high charge neutralization capacity, although their floc formation ability was similar or slightly inferior. However, high-basicity Al(OH)3-dissolution PACl was inferior when the sulfate ion concentration in the raw water was low. Sulfate ions were required in the raw water for high-basicity PACls to be effective in floc formation. In particular, very high sulfate concentrations were required for high-basicity AlCl3-titration PACls. The rate of hydrolysis, which is related to the polymerization of aluminum species, is a key property, besides charge neutralization capacity, for proper coagulation, including formation of large floc particles. The aluminum species in the high-basicity PACls, in particular that produced by AlCl3-titration, was resistant to hydrolysis, but sulfate ions in raw water accelerated the rate of hydrolysis and thereby facilitated floc formation. Normal-basicity Al(OH)3-dissolution PACl was hydrolysis-prone, even without sulfate ions. Aluminum species in the high-basicity AlCl3-titration PACl were mostly those with a molecular weight (MW) of 1-10 kDa, whereas those of high-basicity Al(OH)3-dissolution PACls were mostly characterized by a MW > 10 kDa. Normal-basicity Al(OH)3-dissolution PACl was the least polymerized and contained monomeric species.