2017 OHIO SECTION ANNUAL CONFERENCE

Transcription

1 2017 OHIO SECTION ANNUAL CONFERENCE Toledo, Ohio September 2629, 2017 Applications of CO 3 in Removing Contaminants of Emerging Concern by UV/NO 3 /HCO 3 in Water Reuse and Detoxification Ying Huang 1* Dionysios D. Dionysiou 1 1 Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, Ohio 45221, USA huang2yg@mail.uc.edu

2 OUTLINE INTRODUCTION AND BACKGROUND The Water Treatment Processes for Water Reuse Applications The Problem of Contaminants of Emerging Concern in Reused Water RESULTS AND DISCUSSION Destruction of Selected Contaminants of Emerging Concern by UV/NO 3 /HCO 3 Mechanisms of Removing Selected Contaminants of Emerging Concern by UV/NO 3 /HCO 3 Cytotoxicity of Degraded Contaminants of Emerging Concern by UV/NO 3 /HCO 3 Application of UV/NO 3 /HCO 3 to Remove Contaminants of Emerging Concern from Reverse Osmosis Permeate SUMMARY AND CONCLUDING REMARKS

3 Background: Water reuse typesofwaterreuse/ waterdayn /rebatesfreebies

4 Diclofenac Background (contaminants of emerging concern) Ibuprofen A nonsteroidal anti Cl A nonsteroidal antiinflammatory inflammatory drug (NSAID). LD 50 =390mg/kg (orally in Cl NH OH drug (NSAID). LD 50 =636mg/kg (orally in rate); 740 (orally in mouse). OH mice). O O Triclosan An antimicrobial agent. Potential hazard of Cl endocrinedisrupting Cl O OH Cl Carbamazepine An anticonvulsant pharmaceuticals. LD 50 =1957 mg/kg (orally in rate); 529 (orally in mouse). N chemical. Bisphenol A Atrazine O NH 2 Used in plastic. Potential hazard of endocrinedisrupting HO OH A widely used pesticide. LD 50 =636mg/kg (orally in rate); 740 (orally in mouse). N Cl N chemical. N H N N H A limited number of studies have appeared on the success of removing these compounds with conventional treatments.

5 UVbased AOPs for water reuse applications: UV/H 2 O 2 Example: Wastewater Reuse in Orange County, California, USA Groundwater Recharge for Indirect Potable Reuse Groundwater Replenishment System (GWRS) World's Largest Wastewater Purification System for Indirect Potable Reuse 70 million gallons/day water supplies Secondary Effluent Microfiltration (MF) Reverse Osmosis (RO) H 2 O 2 Ultraviolet Light Seawater Intrusion Barrier Recharge Basins Case_Study Orange_Couny _Water_District.pdf; (Parts of slide courtesy of Dr. Bill Cooper, UCI)

6 UVbased AOPs for water reuse applications: UV/H 2 O 2 Example: Wastewater Reuse in Orange County, California, USA Groundwater Replenishment System (GWRS) Secondary Effluent UV/H 2 O 2 : Microfiltration (MF) Reverse Osmosis (RO) H 2 O 2 Ultraviolet Light HO OH + hv OH + OH (φ=1.0) Advantages: Efficiently generate a lot of strong oxidant, OH. Disadvantages: High cost due to adding extra oxidant, H 2 O 2. Seawater Intrusion Barrier Recharge Basins Case_Study Orange_Couny_Water_Distric t.pdf; (Parts of slide courtesy of Dr. Bill Cooper, UCI)

7 Possibility of applying UV/NO 3 /HCO 3 for water reuse applications Groundwater Replenishment System (GWRS) Secondary Effluent Microfiltration (MF) Reverse Osmosis (RO) Ultraviolet Light Seawater Intrusion Barrier UV/NO 3 /HCO 3 : NO 3 + hv NO 3 NO 3 NO 2 + O 0.63 mm NO 3 Bicarbonate alkalinity as mg CaCO 3 L 1 Recharge Basins O + H 2 O OH + OH OH + HCO 3 CO 3 + H 2 O kk = M 1 s 1 Benedict, K. B.; McFall, A. S.; Anastasio, C., Quantum Yield of Nitrite from the Photolysis of Aqueous Nitrate above 300 nm. Environmental Science & Technology 2017, 51 (8), Mazellier, P.; Leroy, E.; De Laat, J.; Legube, B., Transformation of carbendazim induced by the H2O2/UV system in the presence of hydrogenocarbonate ions: involvement of the carbonate radical. New Journal of Chemistry 2002, 26 (12),

8 Evaluate the application of UV/NO 3 /HCO 3 to degrade selected CECs (a) 1.0 UV alone UV/HCO UV/NO 3 in MilliQ water UV/NO 3 /ph 8.5 buffer UV/NO 3 /HCO 3 Diclofenac Functional Group: aromatic amine 0.6 Cl C/C 0 [Diclofenac] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm NH Cl OH O UV fluence (mj cm 2 ) Diclofenac could be degraded directly by UV photolysis or UV/HCO 3 at ph = 8.5. The degradation extent of diclofenac in UV/HCO 3 was same with that in UV alone at ph = 8.5, indicating the dominant role of direct UV photolysis in UV/HCO 3. Adding HCO 3 significantly improved the degradation efficiency of diclofenac by UV/NO 3 at ph = 8.5.

9 Evaluate the application of UV/NO 3 /HCO 3 to degrade selected CECs (b) 1.0 UV/HCO 3 (c) 1.0 C/C UV/pH 8.5 buffer UV/NO 3 /ph 8.5 buffer UV/NO 3 /HCO 3 [Triclosan] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm C/C [Bisphenol A] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm UV/pH 8.5 buffer UV/HCO 3 UV/NO 3 /ph 8.5 buffer UVNO 3 /HCO UV fluence (mj cm 2 ) UV fluence (mj cm 2 ) Cl OH Triclosan & Bisphenol A O Functional Group: phenolic group Cl Cl HO OH Similarly to diclofenac, the degradation extent of triclosan and bisphenol A in UV/NO 3 could also be accelerated by adding HCO 3.

10 Evaluate the application of UV/NO 3 /HCO 3 to degrade selected CECs (d) Ibuprofen Functional Group: aromatic ring 0.6 C/C 0 OH UV/HCO 3 UV/NO 3 /HCO 3 [Ibuprofen] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm O UV/NO 3 /ph 8.5 buffer UV fluence (mj cm 2 ) Ibuprofen could not be degraded directly by UV photolysis or UV/HCO 3 at ph = 8.5. Adding HCO 3 significantly impressed the degradation efficiency of ibuprofen by UV/NO 3 at ph = 8.5.

11 (e) Evaluate the application of UV/NO 3 /HCO 3 to degrade selected CECs (f) C/C 0 C/C 0 UV/HCO 3 UV/NO 3 /HCO 3 [Atrazine] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm UV/HCO 3 UV/NO 3 /HCO 3 [Carbamazepine] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm UV/NO 3 /ph 8.5 buffer UV/NO 3 /ph 8.5 buffer UV fluence (mj cm 2 ) Cl Atrazine UV fluence (mj cm 2 ) Carbamazepine N H N N N N H Functional Group: Nisopropyl group Nethyl group O N NH 2 Functional Group: double bond aromatic amines Similarly to ibuprofen, the degradation extent of atrazine and carbamazepine in UV/NO 3 could also be impressed by adding HCO 3.

12 Takehome information UV/NO 3 /HCO 3 shows to be effective for the contaminants with phenolic and aromatic amine groups.

13 Identification of reactive species in UV/NO 3 /HCO 3 system C of 4hyroxybenzoic acid (um) [Benzoic acid] 0 = 1 g L 1 [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm UV/NO 3 /ph 8.5 buffer UV/NO 3 /HCO 3 UV/pH 8.5 buffer UV/HCO 3 O In order to identify OH, benzoic acid was used as the probe, the produced 4 hydroxybenzoic acid in different system was measured by HPLC. OH OH O OH UV fluence (mj cm 2 ) OH The amount of OH in direct UV photolysis system at ph 8.5 was similar to that in UV/HCO 3 due to the direct UV photolysis of hydroxyl ions (OH ) at basic conditions. The amount of OH in UV/NO 3 at ph 8.5 was a little bit higher than that in UV/NO 3 /HCO 3 due to the reaction of OH and HCO 3.

14 Identification of reactive species in UV/NO 3 /HCO 3 system (a) 1.0 UV/pH 8.5 buffer UV/NO 3 /10mM MeOH/pH 8.5 buffer 0.8 UV/NO 3 /HCO 3 /10 mm MeOH UV/NO 3 /HCO 3 Then, MeOH was used as the quenching agent for OH to identify CO 3. k OH,MeOH = M 1 s 1 C/C [Diclofenac] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm k CO3,MeOH < M 1 s 1 10 mm MeOH was able to completely quench produced OH by 10 mm NO 3 under UV irradiation UV fluence (mj cm 2 ) The different removal extent of diclofenac by UV/NO 3 /MeOH and UV/NO 3 /HCO 3 at ph 8.5 should be ascribed to the presence of CO 3. Buxton, G. V.; Greenstock, C. L.; Helman, W. P.; Ross, A. B., Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals ( OH/ O) in Aqueous Solution. Journal of Physical and Chemical Reference Data 1988, 17 (2), Chen, S.N.; Cope, V. W.; Hoffman, M. Z., Behavior of carbon trioxide () radicals generated in the flash photolysis of carbonatoamine complexes of cobalt (III) in aqueous solution. The Journal of Physical Chemistry 1973, 77 (9),

15 Identification of reactive species in UV/NO 3 /HCO 3 system (b) 1.0 UV/pH 8.5 buffer UV/NO 3 /50mM MeOH/pH 8.5 buffer (c) UV/NO 3 /HCO 3 /50 mm MeOH UV/NO 3 /HCO C/C [Triclosan] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm C/C UV/pH 8.5 buffer UVNO 3 /50mM MeOH/pH 8.5 buffer [Bisphenol A] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm UV/NO 3 /HCO 3 /50 mm MeOH UV/NO 3 /HCO UV fluence (mj cm 2 ) NO 3 + hv ONOO ϕ = 6.5% UV fluence (mj cm 2 ) 50 mm MeOH was unable to completely quench the produced OH when degrading triclosan and bisphenol A by UV/NO 3, which might be due to the generated peroxynitrite. Peroxynitrite could selectively oxidize contaminants with phenolic group. The different removal extent of triclosan and ibuprofen by UV/NO 3 /MeOH and UV/NO 3 /HCO 3 at ph 8.5 also should be ascribed to the presence of CO 3.

16 Quantification of reactive species in UV/NO 3 /HCO 3 system Using 50 µm of Nitrobenzene (NB) and 50 µm of 4 chlorophenol (4CP) as probes, respectively. d NB dt = kk OH, NB [ OH] ss [NB] +kk CO3, NB[CO 3 ] ss [NB] +0.1 mw cm 2 kk photolysis [NB] ln NB ln NB 0 = (0.1 mw cm 2 kk obs,uv/no 3 /HCO 3 )t Where 0.1 mw cm 2 kk obs,uv/no 3 /HCO 3 = kk OH, NB [ OH] ss + kk CO3, NB[CO 3 ] ss mw cm 2 kk photolysis kk OH, NB [ OH] ss mw cm 2 kk photolysis

17 Quantification of reactive species in UV/NO 3 /HCO 3 system Using Nitrobenzene (NB) and 4chlrophenol (4CP) as probes. [ OH] ss and [CO 3 ] ss were calculated as M and M, respectively. OH ss = 0.1 mw cm2 (kk obs,uv/no 3 /HCO 3 kk photolysis ) kk OH,NB CO 3 ss = 0.1 mw cm2 (kk obs,uv/no 3 /HCO 3 kk photolysis ) kk OH, 4CP [ OH] ss kk CO3, 4CP

18 Takehome information There are two main reactive species in UV/NO 3 /HCO 3, CO 3 and OH. The steadystate concentration of CO 3 is 10 times of the steadystate concentration of OH.

19 Cytotoxicity of treated diclofenac, triclosan, and bisphenol A by UV/NO 3 /HCO 3 (a) Normalized (595650) absorbance UV fluence (mj cm 2 ) [Diclofenac] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm MeOH 5% = 0.83 The higher the bar, the lower the toxicity; Bar below the dashed line indicates the exposure cause >20% mortality. (n=3). Measured by LS180 and MCF7 assay. Cytotoxicity of diclofenac increased after the treatment by UV/NO 3 /HCO 3, which might be due to the formation of transformation products of diclofenac that were more toxic Concentration of target DCF (ppm)

20 Cytotoxicity of treated diclofenac, triclosan, and bisphenol A by UV/NO 3 /HCO 3 (b) Normalized (595650) absorbance UV fluence (mj cm 2 ) [Triclosan] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm MeOH 5% = 0.83 The higher the bar, the lower the toxicity; Bar below the dashed line indicates the exposure cause >20% mortality. (n=3). Measured by LS180 and MCF7 assay Concentration of target TCS (ppm) Cytotoxicity of triclosan did not change after the treatment by UV/NO 3 /HCO 3, which might be due to the formation of transformation products of triclosan.

21 Cytotoxicity of treated diclofenac, triclosan, and bisphenol A by UV/NO 3 /HCO 3 (c) Normalized (595650) absorbance [Bisphenol A] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 3 mm MeOH 5% = Concentration of BPA (ppm) UV fluence (mj cm 2 ) The higher the bar, the lower the toxicity; Bar below the dashed line indicates the exposure cause >20% mortality. (n=3). Measured by LS180 and MCF7 assay. Interestingly enough, cytotoxicity of bisphenol A decreased after the treatment by UV/NO 3 /HCO 3. Further study about the transformation products of bisphenol A would be studied.

22 Takehome information Although the cytotoxicity of treated diclofenac and triclosan did not decrease, the cytotoxicity of treated bisphenol A decreased. The transformation products of diclofenac, triclosan, and bisphenol A will be investigated in the future.

23 Application of UV/NO 3 /HCO 3 to remove selected CECs in RO permeate (a) C/C Atrazine Ibuprofen Carbamazepine Bisphenol A Diclofenac Triclosan [CEC] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 1 mm In RO permeate: 0.63 mm NO 3 Bicarbonate alkalinity as mg CaCO 3 L UV fluence (mj cm 2 ) Degradation of 6 selected CECs by UV/NO 3 /HCO 3 in RO permeate that was collected from Orange County Water District. Triclosan and diclofenac were able to be efficiently removed by UV/NO 3 /HCO 3 in RO permeate after 160 mj cm 2 UV fluence. Bisphenol A might need a little bit more time to be totally removed.

24 (b) 30 Application of UV/NO 3 /HCO 3 to remove selected CECs in RO permeate k obs (x 10 3 cm 2 mj 1 ) UV only UV/NO3 UV/NO3/HCO3 [CEC] 0 = 1 µm [NO 3 ] 0 = 10 mm [HCO 3 ] 0 = 1 mm In RO permeate: 0.63 mm NO 3 Bicarbonate alkalinity as mg CaCO 3 L Diclofenac Triclosan Bisphenol A Ibuprofen Atrazine Carbamazepine Similarly to the degradation processes in MilliQ water, HCO 3 improved the degradation rate of diclofenac, triclosan, and bisphenol A by UV/NO 3, while impressed the degradation rate of ibuprofen, atrazine, and carbamazepine by UV/NO 3. The results indicated that the residual NO 3 and HCO 3 were not sufficient to produce enough reactive species to efficiently remove contaminants even with aromatic amine and phenolic groups.

25 Conclusions CO 3 basedaop shows to be effective for the contaminants of emerging concern with phenolic and aromatic amine groups. In UV/NO 3 (10 mm)/hco 3 (3 mm) system, the steadystate concentration of OH ( M) is lower than that of CO 3 ( ). Although the cytotoxicity of diclofenac and triclosan did not decrease after the treatment of UV/NO 3 /HCO 3 at ph = 8.5, the cytotoxicity of treated bisphenol A was reduced. In RO permeate, the reactive species produced by residual NO 3 and HCO 3 were not sufficient to remove diclofenac, triclosan, and bisphenol A after 160 mj cm 2 UV fluence, but they could be improved by adding NO 3 and HCO 3.

26 Acknowledgements Funding The authors acknowledge financial support from the USGSWRRI (2015SC101G) for this research. Ying Huang acknowledges support from the China Scholarship Council (CSC) scholarship ( ).

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