Nanotechnology-Enabled Water Treatment for improved Food Safety and Public Health

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Nanotechnology-Enabled Water Treatment for improved Food Safety and Public Health A joint study in Swaziland by the Food and Agriculture Organization of the United Nations and Rice University (Houston, Texas)

Water quality and food safety: a global public health priority 884 million people in the world do not have access to safe water (37% in Sub Saharan Africa) 2 million people die annually for causes related to unsafe water, poor sanitation and hygiene. > 1.5 million children < 5 years of age die annually of diarrhoeal disease Diarrhoea kills more children every year than AIDS, and malaria combined

Water contaminants and Food Safety Microbiological contaminants Water can be an important vehicle for transfer of pathogens from human and animal sources into food Chemical contaminants Water can also carry heavy metals from the ground and/or persistent organic pollutants and endocrine disruptors (EDs) from the environment into the food chain Food Safety is strongly linked to the quality of water used at each step of the food chain from production to consumption

Why this study? Ensuring reliable access to affordable and safe sources of water is critical to both global health and economic development. This challenge is rapidly growing as: the world s population increases; global climate change threatens to take away already scarce fresh water resources; agricultural and industrial contamination further limits the availability of adequate water supply; Etc. We need to keep abreast of new technologies as well as of new developments in more conventional systems and see which could offer best opportunities to face these critical issues Among the various technological innovations for water treatment, nanotechnologies are emerging with great potential for water treatment and recycle.

The TECHNOLOGY to be investigated should be based on the criteria of safety, affordability, low maintenance, and minimal energy requirements Source Water Photo-reactive trough/liner reactor 1 O 2 OH

Objectives of the study The FAO collaboration with Rice aims to assess the feasibility of applying an innovative nanotechnology in Swaziland The specific objectives of the study are: 1 Define local conditions including: specific characteristics of the sites volume of water to be treated water quality characteristics Needs and capacities of the final users 2 Generate performance data of the nano-based treatment unit by Evaluating treatment efficiency for the identified priority water contaminants, Evaluating treatment efficiency under local climatic conditions Evaluating the potential food safety and environmental risks arising from the technology Defining best operating conditions of the demo unit 3 Determine the technology potential, feasibility and cost

Study s Activities Survey by a national consultant to collect, review and analyze existing national data on water quality characteristics and other relevant parameters. Analysis of water samples from the selected sites to identify and quantify water contamination First mission to define, the required characteristics of the system, the local context specificities. Generation of performance data of the nano-based treatment unit Final workshop aimed at presenting the study results and discussing with local stakeholder the technology and the alternatives including comparison of the cost and efficiency of this system versus other alternatives

Three dams sites were visited: Mcozini Dam, Lubhuku Dam, and Mlawula Dam Mcozini seemed to offer the best conditions - Water turbidity is high but not so much to require an additional step (like coagulation) before the photo catalysis. - The field area to be watered is not excessive - The site is easily accessible Series of consultations were held: - Local farmers were informed about the study, its objectives and modalities. First mission (April 2012) - National authority (Min of Agriculture) was briefed and informed about the study and its expected outcomes - Other concerned stakeholders (including Swaziland Water Corporation Services) offered additional important information

Study findings Based on the info/data collected through the survey by the national consultant and during the first mission and, Rice University team refined and tested the water treatment technology Let s look at the results

Water Quality Mcozini Dam Lubhuku Dam Mlawula Dam National Standard Irrigation (Drinking) Total coliform 4001.2** 1498.2** 4025.3** 1-10 (0) (per 100 ml) Fecal coliform 87.2** 123.0** 162.0** 1-10 (0) (per 100 ml) Turbidity (NTU) 9.0** 304.6** 202.4** 5 (5) BOD (ppm) 5.5* 1.0 0.7 10 (5) COD (ppm) 19.4* 23.4* 18.0* 75 (10) * indicates value above National drinking water standards ** indicates value above National drinking and irrigation water standards

Survival Ratio (N/N0) Visible light PCs for Liner Virus removal Very efficient Realistic contact times 1.E+01 1.E+00 1.E-01 1.E-02 Virus Inactivation by amino-fullerene PC 1.E-03 1.E-04 1.E-05 AD2 MS2 0 1 2 3 4 5 6 7 8 Irradiation Time (Min)

Relative Concentration Visible light PC for Liner POP Removal Some easily removed Some more recalcitrant Disinfection Poor removal efficiency Combined w/ Sunlight?

Liner Reactor Source Water Opportunities Ease of use/operation No external energy (sunlight and gravity) Longer contact times Drawbacks Only active w/ sunlight (not w/ cloud, at night) Sedimentation Infrastructure

Could the Liner reactor work in the observed context? Source Water Could the Liner reactor work? Add small sedimentation pond Remove pipe system and replace with a trough Very small slope Protected from livestock, etc. Use current pipe system for rinsing trough? Distance is critical (not too close, too far)

Decision: investigate another Photoreactor Option Fluidized bed photoreactor Light Source (lamp) Water out Photocatalyst Water in

Fluidized Bed Photoreactor (FBPR)

Photocatalysis Parameters Materials TiO 2 Fullerenes (C 60 ) Porphyrins Light Source Visible UV-A (350 nm) UV-C (254 nm) Substrates Silica gel Quartz sand Attachment Covalent binding (C 60 ) Heat deposition (TiO 2 ) Sol-gel methods (TiO 2 ) Requirements: Efficiency Stability Reusability Safety

Photocatalytic activity k eff (min -1 *10-4 ) ± one SD Material Attachment Visible Light (400-800 nm) UV-A Light (300-400 nm) UV-C Light (254 nm) Powder (no substrate) 18.1±1.9 548.7±133.8 4766.6±362.5 Sand (heat, H20) 0 29.2±1.3 321.3±23.1 TiO 2 Sand (heat, solvent) 0 0 332.9±52.8 Sand (sol-gel) 0 31.8±3.4 275.5±18.9 Silica (sol-gel) 5.9±0.6 511.5±83.2 491.9±28.8 Fullerenes Silica 68.8±1.0 145.2±1.2 17.0±1.4 Powder (no substrate) 245.2±60.7 215.3±154.7* 0 Porphyrins Silica 11.3±0.4 19.0±1.6 0 *=large error due to limited sample availability (insufficient replicates)

Fullerene Repetition FFA C/C 0 1 0.75 0.5 0.25 UV-C UV-A Visible 0 0 1 2 3 4 5 Number of Repetitions TiO 2 1 FFA C/C 0 0.75 0.5 0.25 UV-C UV-A Visible 0 0 1 2 3 4 5 Number of Repetitions

Degradation % Long-term reuse (TiO 2 ) 2 Months with no loss in efficiency (< 3%) Slight variability after 60+ days (~10%) May have to be replaced after several months 1 0.75 0.5 0.25 Daily Removal Average removal 0 0 20 40 60 80 Days

Titanium Concentration (mg/l) Does the PC leach? During normal use, the effluent titanium concentration was consistently zero, with only two samples measuring any titanium (at the lowest possible detection level-10 µg/l) 0.06 0.05 0.04 0.03 0.02 0.01 Initial Rinse Series2 Avg. Ti conc. in US drinking water 0 0 25 50 75 Volume (L)/Days of use

Relative k value (sec-1) Loading-How much PC? 0.05 0.04 0.03 0.02 0.01 0-0.01 Self-shading (bad) 0 1 2 3 4 5 6-0.02-0.03 PC loading (g/l)

FFA C/C0 Does turbidity have an effect? NO, up to100 NTU 1 0.8 100 NTU 50 NTU Mcozini: 10-20 NTU Other sites: 200-300 NTU 0.6 0.4 0.2 20 NTU 5 NTU 0 0 20 40 60 80 100 120 Time

% E. coli Inactivation Disinfection 90% disinfection in 15 s, 99.9% in 45 s Most of the disinfection comes from UV alone 99.9 90 PC provides incremental added value 0 99 UV alone UV+PC 0 10 20 30 40 50 Time (s)

% Virus Inactivation Virus removal Very little difference between UV alone and UV+PC No added value 99.99 99.9 99 90 0 FBPR UVC Alone UVC + TiO2 0 50 100 150 Irradiation Time (sec)

Carbaryl C/C0 Pesticide and PoP removal 50% removal in 3 min PC removes 2x more pesticide than UV alone Significant added value 0 50 25 UV+PC UV alone 0 1 2 3 Time (min)

Type of system Centralized conventional treatment comparison Treatment cost ($/1000L) Approx. installation cost ($1000) Conventional 1.10 40 Reverse Osmosis 2.78 50 Direct Filtration 1.10 35 Activated Carbon 1.05 100

POU treatment options Type of POU system Treatment cost ($/1000L) Delivered (bottled) 250 water Disinfection tablets 200 Small Reverse 77 Osmosis Carbon-Block 70 filtration UV Disinfection 2 UV Disinfection capital cost: $3,000- $10,000 FBPR capital cost: ~$5,000

Conclusions 1. FBPR with TiO 2 is a promising technology but it currently does not show significantly higher disinfection efficiency over conventional POU treatment systems to merit pilot studies in a second phase. No higher bacterial or viral removal efficiency compared to UV alone, which was very efficient (> 99.9%) and left little room for improvement Enhanced removal of pesticides and possibly other trace organics, but with a contact time on the order of several minutes 2. Explore other options such as Photocatalytic reactive lining What are the merits and limitations of this approach and what interventions and in what scenarios would it be feasible? 3. Prevent the majority of bacterial contamination by fencing reservoirs and utilizing animal troughs

Recommendations Explore PC liner options Feasibility Cost Source Water Other treatment options Commercial UV?

Recommendations Fencing!! Isolate reservoirs Utilize animal troughs Could prevent majority of bacterial contamination