Addition Of Chlorine Research Articles

The transformation of dissolved organic matter and formation of halogenated by-products during electrochemical advanced oxidation pretreatment for shale gas produced water

Electrochemical advanced oxidation processes (EAOPs) have shown great potential for the treatment of shale gas produced water (SGPW). In this study, we investigated the transformation of dissolved organic matter (DOM) during EAOPs of SGPW and the formation of toxic halogenated by-products at various current densities, using fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry. We found that the priority of DOM removal was terrestrial humic-like > microbial humic-like > protein-like substances. Non-Halogenated organic compounds (non-HOCs) and HOCs were predominantly CHO, and CHOCl/CHOBr compounds in EAOP-treated SGPW, respectively. As applied current density and treatment time increased, the production of oxyhalides increased, with chlorate > bromate > perchlorate. Meanwhile, most DOM was mineralized, resulting in residual products with higher modified aromaticity index (AImod) and nominal oxidation state of carbon (NOSC). The resistants had lower mass-to-charge ratio (m/z), AImod, NOSC, and double bond equivalent minus oxygen per carbon ((DBE−O)/C). The dominant reactions were the addition of tri-oxygen and deallyl. Bromine addition dominated the reactions of halogenating addition, while chlorine addition took second place. Furthermore, the acute toxicity of SGPW was positively correlated with inorganic halogenated by-products. This study contributes to the understanding and improvement of EAOPs for the treatment of SGPW.

Leveraging the 3-Chloro-4-fluorophenyl Motif to Identify Inhibitors of Tyrosinase from Agaricus bisporus.

Tyrosinase (EC 1.14.18.1) is implicated in melanin production in various organisms. There is a growing body of evidence suggesting that the overproduction of melanin might be related to several skin pigmentation disorders as well as neurodegenerative processes in Parkinson's disease. Based on this consideration, the development of tyrosinase inhibitors represents a new challenge to identify new agents in pharmaceutical and cosmetic applications. With the goal of identifying tyrosinase inhibitors from a synthetic source, we employed a cheap and facile preliminary assay using tyrosinase from Agaricus bisporus (AbTYR). We have previously demonstrated that the 4-fluorobenzyl moiety might be effective in interactions with the catalytic site of AbTYR; moreover, the additional chlorine atom exerted beneficial effects in enhancing inhibitory activity. Therefore, we planned the synthesis of new small compounds in which we incorporated the 3-chloro-4-fluorophenyl fragment into distinct chemotypes that revealed the ability to establish profitable contact with the AbTYR catalytic site. Our results confirmed that the presence of this fragment is an important structural feature to improve the AbTYR inhibition in these new chemotypes as well. Furthermore, docking analysis supported the best activity of the selected studied compounds, possessing higher potency when compared with reference compounds.

Widespread detection of chlorine oxyacids in the Arctic atmosphere

Chlorine radicals are strong atmospheric oxidants known to play an important role in the depletion of surface ozone and the degradation of methane in the Arctic troposphere. Initial oxidation processes of chlorine produce chlorine oxides, and it has been speculated that the final oxidation steps lead to the formation of chloric (HClO3) and perchloric (HClO4) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO3 and HClO4. Significant levels of HClO3 were observed during springtime at Greenland (Villum Research Station), Ny-Ålesund research station and over the central Arctic Ocean, on-board research vessel Polarstern during the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) campaign, with estimated concentrations up to 7 × 106 molecule cm−3. The increase in HClO3, concomitantly with that in HClO4, was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO3 and HClO4 by hydroxyl radicals. HClO3 and HClO4 are not photoactive and therefore their loss through heterogeneous uptake on aerosol and snow surfaces can function as a previously missing atmospheric sink for reactive chlorine, thereby reducing the chlorine-driven oxidation capacity in the Arctic boundary layer. Our study reveals additional chlorine species in the atmosphere, providing further insights into atmospheric chlorine cycling in the polar environment.

Experimental investigation on dyeing wastewater treatment and by-product hydrogen with a reverse electrodialysis flocculator

Hydrogen production and dye degradation can be achieved simultaneously in a hybrid system of reverse electrodialysis（RED）and electrocoagulation (EC), using current derived from the salinity gradient energy. Under the current, Fe electrode is used as the anode to produce Fe2+(subsequently oxidized to Fe3+) which combines with OH− produced from the cathode to remove the dyes, while the hydrogen gas produced by the cathode is collected by a hydrogen collection device. The experiments are carried out to investigate the effects of different initial concentrations, pH, currents, electrode rinse solution (ERS) flow rates and the addition of chlorine on the degradation rate and hydrogen production. The results indicate that the degradation rate and hydrogen production could reach 98.3% and 150 m h−1 at alkaline condition (pH = 11) and acidic condition (pH = 3) respectively, with a current of 0.4 A. The degradation rate and hydrogen production increase significantly with an increase in current.

UV/chlorine and chlorination of effluent organic matter fractions: Tracing nitrogenous DBPs using FT-ICR mass spectrometry

UV/chlorine process is a promising advanced treatment to eliminate pathogen and remove refractory micropollutants for reclamation of municipal secondary effluent. However, effluent organic matter (EfOM) featuring high organic nitrogen content serves as a potential precursor for nitrogenous disinfection byproducts (N-DBPs) of health concern. The molecular-level alteration of a hydrophobic (HPO) EfOM fraction and a transphilic (TPI) EfOM fraction isolated from the same municipal effluent and the formation of N-DBPs in the UV/chlorine were tracked by ultrahigh-resolution mass spectrometry. Compared with chlorination, UV/chlorine induced a significantly greater modification on the molecular composition of EfOM and resulted in formation of unique formulae and chlorinated molecules with higher degree of oxidation, lower aromaticity, and less carbon number due to the involvement of reactive radical species. For both EfOM fractions, UV/chlorine formed more diverse DBPs with higher intensity and Cl-incorporation than chlorination. The TPI fraction of EfOM characterized by higher O/C and N/C ratios generated more N-DBPs with higher intensity clustered in the high O/C region than the HPO fraction of EfOM by both UV/chlorine and chlorination. Totally, 207 and 117 nitrogen-containing chlorinated formulae were recorded after UV/chlorine treatment of TPI and HPO, respectively. Precursor tracking found a greater number of DBPs were originated from raw EfOM through electrophilic substitution pathway rather than chlorine addition. Toxicity bioassays demonstrated that DBPs can trigger oxidative stress-induced DNA damage, while HPO fraction of EfOM dominated the induction of cytotoxicity. However, no correlation could be established between the diversity/abundance of N-DBPs and the level of DNA damage. A total of 22 DBPs with a significant rank correlation with DNA damage were identified, while C8H6O5NCl was found as the N-DBP with the strongest correlation. The potential toxic chlorine-containing formula with the most abundant intensity was assigned to C5HO3Cl3. This study suggests that the character and transformation of EfOM and associated toxicity is critical to evaluate the UV/chlorine process toward practical application.

Formation of Dichlorine Monoxide for Organic Pollutant Degradation by Free Chlorine in High Chloride-Containing Water

Several ppm levels of free chlorine in high chloride-containing water of no less than 0.20 M show remarkably high degradation rate constants toward carbamazepine (kCBZ′). Dichlorine monoxide (Cl2O) was identified to be responsible for the high kCBZ′. Cl2O degrades aromatic pollutants connected to more electron-donating functional groups faster when comparing kCl2O to 1,4-dimethoxybenzene, bisphenol A, benzoic acid, and CBZ. However, its formation at low free chlorine levels in high chloride-containing water cannot be explained by our current knowledge. We proposed an alternative Cl2O formation mechanism, in which chloride transforms hypochlorous acid/hypochlorite (HOCl/ClO–) to dichlorine (Cl2) and polychloride monoanions (Cln–), which then react with HOCl/ClO– to form Cl2O. Decreasing pH from 8.60 to 4.33 increases Cl2 concentrations and thus generates about 600× higher Cl2O concentrations. Weak acid anions, for example, phosphate and bicarbonate, are strong nucleophiles assisting the Cl2O hydrolysis, but their presence at the testing conditions does not much affect kCBZ′. The proposed alternative Cl2O formation mechanism reveals the roles of chloride in shifting the equilibrium toward the Cl2O formation, allowing the simple chlorine addition strategy to degrade recalcitrant organic pollutants in high chloride-containing wastewater. It may also change our understanding of the speciation of different free chlorine species and their impacts on the DBP formation in high chloride-containing wastewater.

A redox-active inorganic crown ether based on a polyoxometalate capsule.

Cation-uptake has been long researched as an important topic in materials science. Herein we focus on a molecular crystal composed of a charge-neutral polyoxometalate (POM) capsule [MoVI72FeIII30O252(H2O)102(CH3CO2)15]3+ encapsulating a Keggin-type phosphododecamolybdate anion [α-PMoVI12O40]3-. Cation-coupled electron-transfer reaction occurs by treating the molecular crystal in an aqueous solution containing CsCl and ascorbic acid as a reducing reagent. Specifically, multiple Cs+ ions and electrons are captured in crown-ether-like pores {MoVI3FeIII3O6}, which exist on the surface of the POM capsule, and Mo atoms, respectively. The locations of Cs+ ions and electrons are revealed by single-crystal X-ray diffraction and density functional theory studies. Highly selective Cs+ ion uptake is observed from an aqueous solution containing various alkali metal ions. Cs+ ions can be released from the crown-ether-like pores by the addition of aqueous chlorine as an oxidizing reagent. These results show that the POM capsule functions as an unprecedented "redox-active inorganic crown ether", clearly distinguished from the non-redox-active organic counterpart.

Generation, toxicity, and reduction of chlorinated byproducts: Overcome bottlenecks of electrochemical advanced oxidation technology to treat high chloride wastewater

Electrochemical advanced oxidation process (EAOP) is recommended for high-strength refractory organics wastewater treatment, but the accompanying chlorinated byproduct generation becomes a bottleneck that limits the application of this technology to actual wastewater. In this study, we applied EAOP (0.4-40 mA cm−2) to treat ultrafiltration effluent of an actual landfill leachate, and quantitatively assessed the toxicities of the dominant chlorinated byproducts in EAOP-treated effluent. Considering both toxic effect and dose, it followed the order: active chlorine > chlorate > perchlorate > organochlorines. The toxic active chlorine could spontaneously decompose by settling. And secondary bioreactor originally serving for denitrification could be used to reduce perchlorate and chlorate. The effects of residual active chlorine and extra carbon addition on simultaneous denitrification, perchlorate, and chlorate reduction were investigated. It seemed that 20 mg of active chlorine was an acceptable level to bioactivity, and sufficient electron donors favored the removal of chlorate and perchlorate. Pseudomonas was identified as an active chlorine tolerant chlorate-reducing bacteria. And Thauera was responsible for perchlorate reduction under the conditions of sufficient carbon source supply. Our results confirmed that the perchlorate and chlorate concentrations in the effluent below their health advisory levels were achievable, solving the issue of toxic chlorinated byproduct generation during EAOP. This study provided a solution to realistic application of EAOP to treat high chloride wastewater.

Novel synthesis strategy for Z-scheme BiOCl/UiO-66 photocatalyst: Enhanced surface area and improved Cr(VI) removal efficiency

MOF-based photocatalysts with a large specific surface area have been proven to be a potential candidate for removing heavy metal contaminants from the water environment. Herein, we present a much more available Z-scheme BiOCl/UiO-66 composite photocatalyst via a one-step hydrothermal method for efficiently removing Cr(VI) from wastewater. More importantly, when adding bismuth nitrate in the synthesis procedure, BiOCl was in situ generated on the surface of UiO-66 without an additional chlorine source. Experimental results showed that this novel photocatalyst could effectively remove Cr(VI) without adjusting the pH value and adding hole or hydroxyl radical scavengers, which is meant for practical application. Besides, the BET surface area of one-step synthesized BiOCl/UiO-66 composite was considerably extended to 1530.82 m2/g, which is larger than that of two-step synthesized BiOCl/UiO-66 composite and bare UiO-66. Characterization results verified that this one-step synthesized composite's outstanding Cr(VI) photo-removal efficiency was ascribed to increased active sites and improved charge separation and transfer efficiency. This study will likely to provide an effective way to simplify the synthesis procedure of bismuth materials/MOF composites with excellent applications.

The role of chloramines in enhancing soluble manganese removal by manganese contactors by W.R. Knocke, A.M. Weber, P.H. Hargette and E. Odom

Abstract Manganese (Mn) contactors have previously been shown to be quite effective in removing dissolved Mn from drinking water. To date, the contactor media have been regenerated by the application of free chlorine, either continuously in the contactor-applied water or via offline regeneration. This research study was the first to evaluate the potential role of chloramines for the online regeneration of MnOx(s)-coated contactor media. Testing initially at the bench scale and then subsequently over 6 months at the pilot scale demonstrated that chloramines were quite effective at promoting significant media regeneration. Pilot-scale data showed that the presence of chloramines addressed approximately 80% of the media regeneration requirements, allowing for the addition of free chlorine following media backwashing to address the remaining oxidant needs for media regeneration. Hydraulic loading rates of up to 39 m/hr (16 gpm/ft2) could be employed and still produce highly effective Mn removal. The means by which these research results can be applied to other water treatment situations are also discussed.

Catalytic Descriptor Exploration for Ru-Based Fischer–Tropsch Catalysts: Effect of Chlorine and Sulfur Addition

As an important factor in the design of catalysts, catalytic descriptor exploration has emerged as a novel frontier in heterogeneous catalysis. Here, the underlying structure-activity relationships of Ru-based catalysts are theoretically studied to shed light on this area. Calculations of different competing reaction paths suggest that the HCO*-mediated path─because of two synergistic active sites─is more favorable than others. In addition, compared to unadulterated Ru catalysts, the presence of Cl enhances the hydrocarbon production, whereas the presence of S decreases it. After a systematic examination of a series of structure-activity relationships (42 in total), we found that both charge transfer and average charge difference of active Ru atoms are good descriptors for the binding stability of reactants. However, for reactivity the Gibbs free energy of the reactants performs better. More interestingly, due to the quite different catalytic processes of the dissociation and hydrogenation steps, their correlations have opposite slopes.

Effects of increasing chlorine concentration in feedstock on the emission and distribution characteristic of dioxins in circular fluidized bed boiler.

Field studies were conducted to study the emission and distribution characteristics of dioxins by elevating the chlorine concentration in feedstock in a circular fluidized bed boiler. The concentration and total equivalent quantity of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in all flue gas, electrostatic ash, bag filter ash, and bottom ash samples under blank condition (i.e., feedstock was normal coal) and chlorine labeling condition (i.e., feedstock mixed with coal and chlorine-containing labeling agent) were analyzed. Results illustrated that the concentration of PCDD/Fs in all gaseous and ash samples increased with the addition of chlorine in feedstock, with the largest and least increment in dioxin concentration observed in electrostatic ash and flue gas. PCDDs were the predominate congeners in flue gas, accounted for 50.1-60.4% of the total PCDD/F concentration under chlorine labeling and blank conditions, while PCDD/F distribution changed from PCDD- to PCDF-predominate by increasing chlorine content in feedstock under all field test conditions: 46.6-92.9%, 34.0-76.1%, and 47.0-53.1% of PCDFs were distributed in electrostatic ash, bag filter ash, and bottom ash, respectively. Highly chlorinated PCDD/F congeners such as O8CDD/F and 1,2,3,4,6,7,8-H7CDD/F were the primary contributors to dioxin concentration in flue gas and bottom ash samples, whereas low-chlorinated 2,3,7,8-T4CDF and 1,2,3,7,8-P5CDF congeners became critically dominating in electrostatic and bag filter ash.

Enhanced solar inactivation of fungal spores by addition of low-dose chlorine: Efficiency and mechanism

This work demonstrated that the solar inactivation of fungal spores was enhanced by addition of low-dose chlorine. Although the effect of low-dose chlorine alone (2.0 mg/L) on culturability of fungal spores was negligible, the solar/chlorine inactivation on fungal spores performed better than solar alone inactivation, with a lower shoulder length and a higher maximum inactivation rate constant. The enhanced inactivation of Aspergillus niger can be ascribed to the membrane oxidation by chlorine, and the enhanced inactivation of Penicillium polonicum can be ascribed to the membrane oxidation by chlorine and ·OH (·OH plays a major role). The oxidization by chlorine and ·OH led to an increase in membrane permeability of fungal spores, which enhanced the solar inactivation, resulting in an increase in intracellular ROS and more serious morphological damage. Due to the presence of background substances such as dissolved organic matter and metal ions (Fe2+, Mn2+, etc.), the inactivation efficiency in real water matrices was decreased. The main disinfection by-products (DBPs) produced in the inactivation of fungal spores in chlorine alone and solar/chlorine treatments were dichloroacetic acid, trichloroacetic acid, trichloroacetone and trichloromethane. Generally, DBPs formation in solar/chlorine treatment was lower than those in chlorine alone treatment. Moreover, the regrowth potential of the two genera of fungal spores in R2A medium could be inhibited by adding low-dose chlorine.

PENURUNAN COD, BOD, TSS, AMONIA DAN KOLIFORM AIR LIMBAH RUMAH POTONG HEWAN DENGAN BIOFILTER AEROBIC FIXED-BED REACTOR DAN KLORINASI

Slaughterhouses produce wastewater containing high organic matter, which has the effect of polluting water and the surrounding environment. Slaughterhouse wastewater treatment can be done biologically, namely biofiltration, by utilizing microorganisms and chlorination. Efforts in wastewater treatment continue to be developed. This study aimed to determine the effectiveness of biofiltration processing techniques with an Aerobic Fixed-Bed Reactor (AFBR) with pumice stone media combined with chlorination to reduce the levels of COD, BOD, TSS, ammonia, and coliform bacteria. The method applied was to use biofilms from the seedings on pumice with variations of with or without the addition of active suspension, aeration system treatment with time variations, and the addition of chlorine with variations of active chlorine doses. The results showed that the addition of active suspension in the process produced the best biofilm, and was effective in reducing the levels of COD, BOD, TSS, and ammonia. The best reduction of COD levels was at the 36th hour at 81.60 mg/L with an efficiency of 57.45%, BOD at the 36th hour was 24.67 mg/L with an efficiency of 65.74%, TSS at the 42nd hour was 54.0 mg/L with an efficiency of 85.66%, and ammonia at the 42nd hour of 1.5539 mg/L with an efficiency of 88.29%. Chlorination after the treatment with AFBR resulted in a decreased number of coliform bacteria from 1,100 MPN/100 mL to 0 MPN/100 mL with 100% efficiency. The chlorination process resulted in the optimum chlorine dose of 165 ppm with a chlorine residual of 28.80 mg/L. Thus, the treatment for 36-42 hours on AFBR followed by chlorination with a chlorine dose of 165 ppm was relatively effective in reducing COD, BOD, TSS, ammonia, and coliform levels of bacteria in slaughterhouses wastewater.
 Keywords: ammonia, biofiltration, chlorination, coliform.

Comparative cytotoxicity induced by parabens and their halogenated byproducts in human and fish cell lines

Parabens are a group of para-hydroxybenzoic acid (p-HBA) esters widely used in pharmaceutical industries. Their safety is well documented in mammalian models, but little is known about their toxicity in non-mammal species. In addition, chlorinated and brominated parabens resulting from wastewater treatment have been identified in effluents. In the present study, we explored the cytotoxic effects (EC50) of five parabens: methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BuP), and benzylparaben (BeP); the primary metabolite, 4-hydroxybenzoic acid (4-HBA), and three of the wastewater chlorinated/brominated byproducts on fish and human cell lines. In general, higher cytotoxicity was observed with increased paraben chain length. The tested compounds induced toxicity in the order of 4-HBA < MP < EP < PP < BuP < BeP. The halogenated byproducts led to higher toxicity with the addition of second chlorine. The longer chain-parabens (BuP and BeP) caused a concentration-dependent decrease in cell viability in fish cell lines. Intriguingly, the main paraben metabolite, 4-HBA, proved to be more toxic to fish hepatocytes than human hepatocytes by 100-fold. Our study demonstrated that the cytotoxicity of some of these compounds appears to be tissue-dependent. These observations provide valuable information for early cellular responses in human and non-mammalian models upon exposure to paraben congeners.

The biogeochemical cycling of chlorine.

Chlorine has important roles in the Earth's systems. In different forms, it helps balance the charge and osmotic potential of cells, provides energy for microorganisms, mobilizes metals in geologic fluids, alters the salinity of waters, and degrades atmospheric ozone. Despite this importance, there has not been a comprehensive summary of chlorine's geobiology. Here, we unite different areas of recent research to describe a biogeochemical cycle for chlorine. Chlorine enters the biosphere through volcanism and weathering of rocks and is sequestered by subduction and the formation of evaporite sediments from inland seas. In the biosphere, chlorine is converted between solid, dissolved, and gaseous states and in oxidation states ranging from -1 to +7, with the soluble, reduced chloride ion as its most common form. Living organisms and chemical reactions change chlorine's form through oxidation and reduction and the addition and removal of chlorine from organic molecules. Chlorine can be transported through the atmosphere, and the highest oxidation states of chlorine are produced by reactions between sunlight and trace chlorine gases. Partial oxidation of chlorine occurs across the biosphere and creates reactive chlorine species that contribute to the oxidative stress experienced by living cells. A unified view of this chlorine cycle demonstrates connections between chlorine biology, chemistry, and geology that affect life on the Earth.

Characterization of 17 unknown ketamine manufacturing by-product impurities by UHPLC-QTOF-MS.

This study initially reported the selection and characterization of 17 unknown impurities attributed to the manufacture process of ketamine. A total of 150 seized ketamine samples were investigated through ultra-high-performance liquid chromatography-quadrupole-time of flight (UHPLC-Q-TOF). Seventeen characteristic impurities were selected in accordance with four criteria: The compound was detected in over 10% of all 150 seized ketamine samples, the compound had at least one nitrogen, the unsaturation of the compound was more than 5, and the compound was stable in the dilution solvent solution for 48h. The accurate masses of the protonated molecules and product ions of the target impurities were obtained based on the full scan mode and the product ion mode of Q-TOF, respectively. Lastly, the possible structures of the above impurities were tentatively elucidated in accordance with the synthetic route of ketamine, protonated molecules, and MS2 product ions. All 17 impurities had the same skeleton of deschloroketamine (DCK), but were substituted with additional chlorine, hydroxyl, methyl, cyclohexane, and o-chlorophenyl cyclopentyl ketone substituents. Under the electrospray ionization (ESI), the above impurities showed similar characteristic fragment ions through the dissociation of the CH3NH2, C2H6NH, H2O, CO, C2H4O, C4H6, and C2H2 moieties. The above impurities have been routinely used for the profiling analysis of seized ketamine samples in the National Narcotics Laboratory of China and employed to establish the tactical intelligence for law enforcement agencies.

Effect of Chlorine Addition on Texture and Superconducting Performance of YBa2Cu3O7−δ-Coated Conductors

YBa2Cu3O7−δ (YBCO) thin films with the addition of Cl were prepared on Hastelloy tape by the extremely low fluorine metal-organic deposition (MOD) technique. The composition and microstructure of the present samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was revealed that the Cl-added YBCO thin films achieved better texture and density compared with the pure YBCO films. The superconducting properties at magnetic fields were measured using the magnetic property measurement system (MPMS). The results showed that the sample onset transition temperature (Tc, on) did not change significantly after the addition of Cl. The critical current density (Jc) in the presence of YBCO with the addition of Cl increased significantly. Meanwhile, both the Jc and gravitational force (Fp) of the (Cl, Hf) co-added YBCO films were further enhanced at different magnetic fields. The thermodynamic analysis of the BaCO3 removal reaction revealed that the addition of Cl to YBCO formed chlorine compounds, which were effective in avoiding the formation of BaCO3. Further, the calculation results of the Gibbs free energy at different pressure quotients showed that the stability of the relevant chlorine compounds occurred in the order of BaCl2 &gt; CuCl2 &gt; YCl3 and the oxidation of BaCl2 to BaO required a higher temperature compared to BaF2, implying the potential advantages of inhibiting the a-axis growth.

Elimination of Clogging of a Biogas Slurry Drip Irrigation System Using the Optimal Acid and Chlorine Addition Mode

As an emerging contaminant, the clogging substances of emitters in biogas slurry drip irrigation systems affect the efficient return and utilization of biogas slurry to the field to a great extent. This can be prevented using acid and chlorination as engineering measures. Through a hydraulic performance test and sampling detection and analysis, under the same acid addition conditions (pH = 5.5–6.0), three chlorine addition concentrations (0, 1–3, and 4–9 mg/L) and four chlorine addition cycles (6, 10, 14, and 20 days) were tested, aimed to clarify the influence of acid and chlorine addition parameters (chlorine adding cycle, chlorine adding concentration, etc.) on the anti-clogging performance of emitters in biogas slurry drip irrigation system. The results showed that compared with no acid and chlorination treatment (CK), only acid and a reasonable combination of acid and chlorination can significantly reduce the probability of serious and complete clogging of biogas slurry drip irrigation emitters, and they can stabilize the relative average flow of emitters by more than 75%. The measures of adding acid and chlorine change the distribution characteristics of clogging substances at the front and rear of the drip irrigation belt. Furthermore, they promote the migration of clogging substances to the rear of the drip irrigation belt, facilitating the clogging of emitters located thereat. The measures of acid addition and sequential addition of acid and chlorine significantly inhibit the growth of an extracellular polymer in the emitter, and the effect of inhibiting the increase in extracellular polymer concentrations is relatively poor when the acid addition period is excessively long or short. There exists a negative correlation between the extracellular polymer content in the emitter and the change in the emitter flow. Based on the obtained results, to ensure excellent anti-clogging performance of biogas slurry drip irrigation systems, for acid-only treatment measures, the acid dosing cycle is recommended to be 10 days. When acid and chlorination measures are implemented sequentially, the acid chlorination cycle is recommended to be 14 and 10 days when the chlorine concentration is 1–3 and 4–9 mg/L, respectively. This study has important scientific significance and practical value for the establishment of long-term operation management and protection technologies of large-scale biogas slurry drip irrigation systems.

A balancing act: Optimizing free chlorine contact time to minimize iodo-DBPs, NDMA, and regulated DBPs in chloraminated drinking water

Many drinking water treatment plants in the U.S. have switched from chlorination to chloramination to lower levels of regulated trihalomethane (THM) and haloacetic acid (HAA) disinfection byproducts (DBPs) in drinking water and meet the current regulations. However, chloramination can also produce other highly toxic/carcinogenic, unregulated DBPs: iodo-acids, iodo-THMs, and N-nitrosodimethylamine (NDMA). In practice, chloramines are generated by the addition of chlorine with ammonia, and plants use varying amounts of free chlorine contact time prior to ammonia addition to effectively kill pathogens and meet DBP regulations. However, iodo-DBPs and nitrosamines are generally not considered in this balancing of free chlorine contact time. The goal of our work was to determine whether an optimal free chlorine contact time could be established in which iodo-DBPs and NDMA could be minimized, while keeping regulated THMs and HAAs below their regulatory limits. The effect of free chlorine contact time was evaluated for the formation of six iodo-trihalomethanes (iodo-THMs), six iodo-acids, and NDMA during the chloramination of drinking water. Ten different free chlorine contact times were examined for two source waters with different dissolved organic carbon (DOC) and bromide/iodide. For the low DOC water at pH 7 and 8, an optimized free chlorine contact time of up to 1 h could control regulated THMs and HAAs, as well as iodo-DBPs and NDMA. For the high DOC water, a free chlorine contact time of 5 min could control iodo-DBPs and NDMA at both pHs, but the regulated DBPs could exceed the regulations at pH 7.