Characterizing The Fate And Transport Of Chemicals Of Emerging Concern (CEC’s) From Animal Manures...
-
Upload
national-institute-of-food-and-agriculture -
Category
Environment
-
view
71 -
download
0
Transcript of Characterizing The Fate And Transport Of Chemicals Of Emerging Concern (CEC’s) From Animal Manures...
1
Dr. Lance Schideman, Dr. Yuanhui Zhang, Dr. Micheal Plewa, John ScottYoung-Hwan Shin, Peng Zhang, Justin Pals University of Illinois at Urbana - Champaign
Characterizing the fate and transport of bioactive chemicals of emerging concern (CECs) from animal manure during waste-to-energy processes
Problem/Opportunity Statement
2
Manure can be viewed as a problem… Excess nutrient runoff and spills can lead to eutrophication and hypoxia
Hormones can lead to endocrine disruption (e.g., fish feminization) Antibiotics can lead to antibiotic resistance (80% for livestock)
Manure can be viewed as an opportunity…
Big supply- 50 to 150 million dry tons/yr
Manure organics have a large energy content (1-2 Quadrillion BTU) Non-potable water reuse potential
Liquid portion of animal manure (LPAM) ~1 Billion tons/yr Nutrients can be used to grow additional bioenergy feedstocks Manure nutrients reduce cost & CO2 emissions for synthetic fertilizers
Antibacterial Drug Use (FDA, 2009)
Livestock animals Feeding with antibiotics
Storage of livestock manure (Pit or Lagoon)
Manure spreading in the field
River or Lake water Fish feminization Antibiotic resistant infection
Runoff/Drainage/flooding from soil to surface water
Antibiotics, Antibiotic resistant bacteria, and hormones
o Integrated manure management and bio-energy recovery system can interrupt transport
of CECs and thus reduce negative effects on the health of humans & ecosystems
INTRODUCTIONHow CECs in the livestock manure can affect health of humans & ecosystems?
Interrupt transport of CECs with Waste-to-energy system
Overall process diagram for integrated waste to energy system
4
a) swine manure storage, b) LPAM production, c) biomass production, and d) hydrothermal biomass conversion processes.
a)
b)
c)
d)
RESEARCH TOPICS & OBJECTIVES
5
Characterize CECs in the liquid portion of animal manure (LPAM)
Fate of CECs in biological & adsorptive water treatment processes
Mixed algal/bacterial bioreactor (MABB)
Conventional activated sludge (CAS)
With and without granular activated carbon (GAC) incorporated
Fate of CECs in hydrothermal biofuel conversion processes
Hydrothermal liquefaction (HTL) biomass to bio-crude oil
Catalytic hydrothermal gasification (CHG) biomass to syn-gas
HTL of biomass & CHG of HTL-wastewater
Dynamic process modeling describing the fate of bioactive CECs
6
Operating conditions for bioreactors
Mixed Algal-
Bacterial Bioreactor (MABB)
Conventional Activated Sludge Bioreactor (CAS)
Reactor type Sequencing Batch Reactor
Sequencing Batch Reactor
Operating Volume (gal) 50 50
Light intensity (µmol photons/m2/s) 350 -
Temperature (˚C) 18 16
Aeration rate (L/min) 6 11
Organic Loading Rate (mg/L) 48.6 - 571 48.6 - 571
HRT (day) 1- 4 1- 4
SRT (day) 25 – 30 25 - 30
Fill volume ratio (VF/VT, %)
Estrogen Spike Conc(mg/L)
50
1.3 – 396
50
1.3 – 396
MATERIALS & METHODS- Capture of bioactive CECs
MABB
7
Estrogens were well captured in both bioreactors
84.3% - 99.9% removal MABB had slightly higher average
removal than CAS + 5.1 % removal
Reactors with GAC had slightly higher average removal
+ 4.2 % removal % Removal very similar during high
and low spiking events Used for STELLA modeling
RESULTS & DISCUSSION- Capture of bioactive CECs
MABB w/ GAC
MABB w/o GAC
CAS w/ GAC
CAS w/o GAC75
80
85
90
95
100
105Low spikingHI spiking
E2 %
rem
oval
(Ce/
C0)
Hydrothermal liquefaction (HTL) directly converts wet biomass into crude oil
8
Gas Product
Post-HTLWW
Oil Product
Solid Residue
Demonstrated HTL Feedstocks
Reactor
High T:200 – 350 oC High Pressure : 80 – 120 atm
Municipal sludgeManureAlgae
Crop residuesWoody materials
Eout : Ein > 3:1 at lab-scale (% solids =20%)Eout : Ein > 10:1 w/ heat exchangers in commercial applications
HTL successfully converted captured LPAM organics to bio-crude oil
• Biomass % solids = 20%, • HHV of biomass (dry) =
14,140 kJ/kg• Optimal operating condition
was 300 oC & 60 min reaction time• Oil HHV = 31,426 kJ/kg• Energy recovery = 80%
200 60 250 30 250 60 300 30 300 60 350 30 350 600%
10%
20%
30%
40%
50%
60%
70%
Bio-crude oil and solid residue yield of LPAM biomass via HTL
oil solid residue
10
RESULTS & DISCUSSION- HTL destruction of bioactive CECs
250°C/60min
300°C/30min
300°C/60min
350°C/60min
400°C/60min0
20
40
60
80
100
120 E2 removal E1 removal
% R
emov
al
Most HTL operating conditions provide high % removal of hormones
300 ˚C / 60min showed more removal of hormones than 300 ˚C / 30min
Removal was more sensitive to Reaction time than temperature
% Removal of E1 and E2 under various Hydrothermal Liquefaction conditions
11
RESULTS & DISCUSSION- CHG destruction of bioactive CECs All CHG conditions provided high % removal of E1 & E2 ( > 99% removal)
Higher than 450 ˚C, more than 99.87% of E1 and E2 removed
CHG Removal of CECs was more sensitive to temperature than retention time
% Removal of E1 and E2 during the CHG processes for different operating conditions
350°C/60min
400°C/60min
450°C/60min
500°C/60min
550°C/60min98.4
98.6
98.8
99.0
99.2
99.4
99.6
99.8
100.0
100.2 E1 removal E2 removal
% R
emov
al
12
RESULTS & DISCUSSION- Destruction of Florfenicol by HTL
Detection limit of Florfenicol (FF) was 0.05 mg/L in high resolution GC/MS
99.9% of FF in DI water and LPAM were removed with HTL at 300 ˚C and 30 min
Removal of Florfenicol in the HTL process with DI water and LPAM
Florfenicol in LPAM (Post-HTL)
Florfenicol in DI water (Pre-HTL)
Florfenicol in LPAM (Pre-HTL)
Florfenicol in DI water (Post-HTL)
13
RESULTS & DISCUSSION- Florfenicol (FF) breakdown products
4-MSB was the predominant FF breakdown product in the Post–HTL wastewater (5-30%)
4-MSAP and MPS were also detected at higher temperature
14
RESULTS & DISCUSSION- Antibiotic resistance effects
Sensitive Antibiotic
Resistance Assay was
developed
Antibiotic Resistance
occurred when the
positive and negative
control varied
LPAM contributed to
antibiotic resistance
HTL & CHG processes
eliminated the capacity
of LPAM to induce
antibiotic resistance
Antibiotic Resistance fluctuation assay before & after HTL or CHGM
ean Num
ber Antibiotic R
esistance E
.coli W
ells (R
esistant Jackpot Wells/96-W
ell Microplate)
0
10
20
30
40
50
Comparison of different bio-energy processes
• HTL-CHG process was most favorable in terms of net energy yield, assuming heat exchange at 80% efficiency,
• Additional CHG(600C) after HTL can recovery the energy in PHWW at about 7% of total biomass
• Biomass not fully converted to energy products (oil and gas) in direct CHG process
• Significant decrease in oil yield (40% for HTL, 15% for direct CHG) and thus overall energy yield
HTL HTL-CHG Direct CHG
Reaction condition
300C 60min
HTL: 300C 60min
HTL: 300C 60min 400C 60
minCHG: 400C 60min
CHG: 600C 60min
Oil energy yield, kJ/g wet BM
2.45 2.45 2.45 0.98
Gas energy yield, kJ/g wet BM
n.a. 0.22 0.59 0.34
Net total energy
yield, kJ/g wet BM
2.26 2.24 2.46 1.00
Final Aq Product
COD, mg/L96,000 20,000 3,000 52,000
Net Energy recovery 80% 79% 87% 35%
16Dynamic System Modeling with STELLA
A process
Internal FlowsExternal InputOutput
E2-Energy process model construction simulating CECs flow
Waste Pretreatment
Excretion
Bioenergy Conversion(HTL)
Adsorption and Biological Treatment
CHG CHG conversion
BiomassHarvest
HTL destruction/ transformation
Biological degradation/uptake
Physical/chemical adsorption
Discharged in treated WW
Concentrated
biosolid
Dilute
d liq
uid
> 99.9% of hormones can be removed in the integrated treatment system
RESULTS & DISCUSSION- Modeled System CEC removal
Bottom slurry
Screened slurry
Bag filtraion
LPAM (MF)
MABB effMABB eff_recycle 1
MABB eff_recycle 2
MABB eff_recycle 3
MABB eff_recycle 4
% R
emoval of E
2 0
20
40
60
80
100
120E
2 concentration (ng/L)
0
2000
4000
6000
8000
10000
12000
14000
16000
18000% removal % removal of each step E2 concentration (ng/L)
Conclusions
LPAM: Liquid Portion of Animal Manure containing nutrients and dissolved
organics (including bioactive CECs) can become a valuable resource
>98% of CECs in LPAM can be captured w/ an adsorptive-biological reactor
Using algae and GAC enhance the uptake of organics
>99.9% CEC removal possible with optimized multi-step system
> 85% of the energy content of LPAM can be harvested by hydrothermal
biofuel conversion processes
Antibiotics are broken down sufficiently by hydrothermal processes to
eliminate the development of antibiotic resistance
Effluent LPAM is cleaned up significantly for improved surface water quality
or potential water reuse applications
2
19
20
Range of E2 & E1 in swine manure slurry (UIUC) was lower than previous studies (Fine et al., 2003;
Hanselman et al., 2003; Irwin et al., 2001; Raman et al., 2004; Shappell et al., 2007; Sim et al., 2011; Singh et al., 2013).
Spiked concentrations of E1 & E2 were in the range of practical concentration of hormones.
E1 & E2: 1.3 µg/L (low spiking) < real LPAM << 396 µg/L (High spiking) << 3214 µg/kg
gSlurryfSlurry
sSlurrybSlurry
fSlurry pit(Lit)
fLagoon(Lit)
bSlurry(Lit)
sSlurry(Lit)0
500
1000
1500
2000
2500
3000
E2 in slurry E1 in slurry
conc
entr
ation
(μg/
kg )
E2: 27.26 ±0.58 E1: 25.95 ±0.59
RESULTS & DISCUSSIONS Occurrence of hormones
22
Fini
shin
g
Farr
owin
g
Ges
tatio
n
Lagoon
Ⓐ Ⓑ
Ⓒ
INTRODUCTION
Sampling points of swine manure at SRC (Swine Research Center at UIUC)
23
Conventional Pig production cycle
INTRODUCTION
<Source: http://www.epa.gov/agriculture/ag101/porkglossary.html>
Pork glossarya) Breeding: producing offspring
b) Gestation: period when sow is pregnant
c) Farrowing: period from birth to weaning
d) Weaning: removal of piglets from their mother
e) Piglet: young pig
f) Finishing: growing piglets to market weight
g) Heat: estrous period of sow
h) Slaughter: killing pigs
i) Boar: Castrated male pigs
(a)
(b)
(c)
(d)
(e)
(f) (g)
- Fresh solid, urine, slurry, & LPAM
Finishing
Reproduction cycle of sows Life cycle of growing pigs
Breeding
* Sampling points
Gestation
- Manure slurry from Top & sludge
layer at finishing pit
(d)
(h)
24
MATERIALS & METHODSAnalytical methods
24
Swine manure samples Centrifugation Extraction
Evaporation & concentrationELISA or GC/MS analysis at ng/L level
Figure. 2 Flow diagram of the samples preparation and analytical methods of estrogenic hormones
11/5/20132/18/2014
2/26/20143/20/2014
5/21/20147/24/2014
0
1000
2000
3000
4000
5000
6000
7000
0
50
100
150
200
250
300
350
400
450
500sCOD TN TP
Date
sCOD
(mg/
L)
TP &
TN
(mg/
L)
The water quality parameters of LPAM showed seasonal variation based on temperature
sCOD, TN & TP of 6 different LPAM increased with temperature of manure storage
sCOD of LPAM was adjusted to 4,000 mg/L to make bioreactor feedstock
RESULTS & DISCUSSIONS Water quality analysis
Chinese Hamster Ovary (CHO) cell assay (Hsie AW, 1975; Wagner et al., 1998) used
to investigate cytotoxicity of LPAM
Organics in LPAM has a cytotoxicity index of 2.38 which is less toxic than raw
municipal wastewater (8.8), primary effluent (3.8) and secondary wastewater effluent
(2.64)
RESULTS & DISCUSSIONS
0
1
2
3
4
5
6
7
8
9
108.8
3.83.3
2.64 2.38095238095238
Cyto
toxi
city
Inde
x (L
C50)
-1(1
0)3
Figure. 5 Comparison of Cytotoxicity index for LPAM & municipal wastewater
Figure. 4 Cytotoxicity of LPAM organics via CHO cell assay
Sorption onto biomass (E2 >90%) is dominant
Desorption of E2 from the biomass is insignificant (Andaluri et al., 2012)
Biotransformation could be occurred in the bioreactors by microorganisms
INTRODUCTIONRemoval of estrogenic hormones during biological processes
Proposed transformation pathway of estrogenic hormones (Lee & Liu 2002; Hutchins et al., 2007)
28
MABB shows similar sCOD & higher TP removal than CAS with lower aeration
Aeration rate: CAS (11 LPM) & MABB (7 LPM)
60 ~ 65% of sCOD was removed within 3 hours of operation in each reactor
TP removal ratio of each reactor was MABB ( 16.9%) & CAS (4.47%) in 3 hours
0 30 60 90 120 150 180 2100
50
100
150
200
250
CAS MABB
Time (min)
sCO
D (m
g/L)
0 30 60 90 120 150 1800
5
10
15
20
25
30
MABB CAS
Time (min)
TP (m
g/L)
RESULTS & DISCUSSIONSProfile of sCOD & TP removal in one cycle of MABB & CAS
29
RESULTS & DISCUSSIONSProfile of hormones removal in one cycle of MABB operation
Within 11 hours, 88 ~ 96 % of total hormones were removed in both of reactors
GAC addition accelerate & increase the removal of hormones in the MABB
% removal of total hormones in 1 cycle was 98.2 ~ 99.4%
0 500 1000 1500 2000 25000
100
200
300
400
500
600
700
E2 E1 E3 Total EE2
Time (min)
conc
entr
ation
(μg/
L)
0 500 1000 1500 2000 25000
100
200
300
400
500
600
700
E2 E1 E3 Total EE2
Time (min)
conc
entr
ation
(μg/
L)
Figure. 7 Removal of estrogenic hormones in mixed algal-bacterial bioreactor without Granular Activated Carbon (GAC)
Figure. 6 Removal of estrogenic hormones in mixed algal-bacterial bioreactor with Granular Activated Carbon (GAC)
sCOD removal from LPAM ranged from 58.4% to 80.9% with increasing organic
loading from 42.3 to 152 mg/L/day
High Shock loading w/ GAC shows fast recovery (450 mg/L << 2370 mg/L)
≈≈
0
200
400
600
800
1000
1200
1400
1600
1800
50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210
CO
D (m
g/L
)
Time (d)
COD infCOD eff
Phase I-A Phase I-B Phase II Phase III
Shock loading450 & 2370 mg/L
Low LPAM loadingAvg OLR: 42.3 mg/l/d
Mid LPAM loadingAvg OLR: 152 mg/l/d
Low LPAM loadingAvg OLR: 46.5 mg/l/d
68% removal
58.4% removal
80.9% removal
Reactor broken
RESULTS & DISCUSSIONSLong – term operation of Mixed algal-bacterial bioreactor
Phase I-B Phase II
% removal NH4
+-N: 98.4 % removal TN: 41.1NH4
+- N: 94.8
% removal TN: 43.9NH4
+-N: 85.8
Total Nitrogen (415 ~ 833mg/L) of LPAM feedstock was removed up to 44% in
the effluent of MABB
NH4+-N (113.5 mg/L ) of LPAM feedstock were removed up to 98.4% in the
effluent of MABB
Long – term operation of Mixed algal-bacterial bioreactor RESULTS & DISCUSSIONS
32
Low & high spiking in bioreactors were tested for STELLA modeling
Similar % removal of hormones except E1 in MABB w/o GAC
% removal of E1 in algal pre-treatment and HTL ranged from 43.63 to 76.20% (Pham et al., 2012)
RESULTS & DISCUSSIONS
MABB w/ GAC
MABB w/o GAC
CAS w/ GAC
CAS w/o GAC82
84
86
88
90
92
94
96
98
100
102Low spikingHI spiking
E1 %
rem
oval
(Ce/
C0)
MABB w/ GAC
MABB w/o GAC
CAS w/ GAC
CAS w/o GAC75
80
85
90
95
100
105Low spikingHI spiking
E2 %
rem
oval
(Ce/
C0)
33
RESULTS & DISCUSSIONS
Cytotoxicity was decreased in the effluent of MABB
After the spiking of CAS, cytotoxicity was increased in the effluent of reactors
Antibiotics in the spiked feedstock could kill most of the nitrifying bacteria in CAS
Cytotoxicity was increased after the addition of GAC to each reactor
250 300 350 Wastewater Treatment Groups
CH
O C
ell Mean C
ytotoxicity Index Value
(LC50
-1)(10
3) ±SE
<---- Less Toxic ------ More Toxic ---->
0.1
1
10
100
1000
Figure. 12 CHO cell Cytotoxicity Index Values (CTI) of the analyzed samples
a. Sample 4 & 12: LPAM from top/bottom of finishing pit
b. Sample 13 & 14: Effluent from MABB with/without GAC
c. Sample 15 & 16: Effluent from CAS with/without GAC
d. Sample 24: Lagoon wastewater
e. Sample 25: LPAM from bottom of finishing pit
Y D
ata
0
10
20
30
40
50
1. Algal-bacterial bioreactor captured >65% of LPAM organics in one cycle and MABB is more
energy effective process than CAS with lower aeration & free light energy
2. Algal-bacterial bioreactor captured > 98.4% of NH4+-N and > 44% of TN from LPAM in one
cycle, and the removal increased with the addition of GAC
3. Granular Activated Carbon (GAC) can protect and stabilize the reactor from shock loading
4. Algal-bacterial bioreactor removed > 98.2% of estrogenic hormones from LPAM
5. GAC can accelerate & increase the removal of hormones in MABB & CAS
6. Activation of conjugated hormones might increase hormone concentrations in CAS without
GAC
7. Low & high CECs spiking in bioreactors were tested for STELLA modeling, and GAC
contribute to increase the removal of E1 & E2 in each MABB & CAS reactor
CONCLUSIONS
35
INTRODUCTION
Properties 17β-estradiol 17α-estradiol Estrone Estriol FlorfenicolUsed abbreviation E2 EE2 E1 E3 FFClass Steroid Steroid Steroid Steroid AntimicrobialCas registry number 50-28-2 57-63-6 53-16-7 50-27-1 73231-34-2Molecular weight (g/mol) 272.3 296.4 270.4 288.4 358.21Vapor pressure (Pa) 3 x 10-8 6 x 10-9 3 x 10-8 9 x 10-13 NegligibleWater solubility (20°C, ppm) 3.9 - 13.3 4.8 0.8 - 12.4 3.2 - 13.3 over 400mg/L at pH > 5.5
pKa 10.5 - 10.7 10.21 10.3 - 10.8 10.4 9.03log Kow 3.1 - 4.0 3.67, 4.15 3.1 - 4.0 2.6 - 2.8 2.36
Molecular formulaC18H24O2
C20H24O2 C18H22O2 C18H22O3 C12H14Cl2FNO4S
Structure
Characteristics of emerging contaminants
Transformation pathways of estrogenic hormones• Transformation and breakdown of hormones
under hydrothermal processes
• To understand removal of hormones in
hydrothermal processes, we need to know the
change of each concentration of hormones
Proposed transformation pathway of estrogenic hormones (Lee & Liu 2002; Hutchins et al., 2007)
36
Small batch reactor
• Optimization of Hydrothermal processes for CECs removal & Energy
• HTL/CHG/Combined HTL & CHG• Efficiency of CECs removal & Energy recovery• Total Volume (ml): 40 • Working Volume (ml): 20• Organic content (%): 25 ~ 30
ConnectorBody: reactor
Gas inlet
Gas control valve
MATERIALS & METHODS
37
MATERIALS & METHODSAnalytical methods
37
PHWW/PCWW samples Centrifugation Extraction
Evaporation & concentrationGC/MS analysis ng/L level at ISTC
Figure. 2 Flow diagram of the samples preparation and analytical methods of estrognic hormones
38
RESULTS & DISCUSSIONS
Cytotoxicity: 250 ˚C and 300 ˚C < 350˚C
Toxicity in PHWW is proportional to temperature
Higher energy yield shows less cytotoxicity
Modification of HTL conditions may affect the cytotoxicity of PHWW
Figure 2. CHO cell cytotoxicity index values for each PHWW sample
250 300 350 250 ˚C 300 ˚C 350 ˚C
More toxic
39
CONCLUSIONS
1. Highest Bio-crude oil yields of HTL at 300˚C /60 min
2. Hormones removal is more sensitive to Reaction time than temperature
3. 300 ˚C /60 min is effective operating condition for HTL to provide simultaneous
bioenergy production and removal of hormones, COD and cytotoxicity
4. Chrome, Arsenic, Zinc, Cadmium, and Lead were removed up to 99.6% removal
after HTL
HTL
CHG1. Highest Bio-crude oil yields of HTL at 300˚C /60 min
2. Removal of CECs is sensitive to temperature in CHG
3. Ra-Ni was the most effective catalyst to remove estrogenic hormones
4. Amount of catalyst doesn’t affect the removal of hormones
5. Ru & Ru/NaOH shows the highest COD removal
Acknowledgement
Project team
• Dr. Lance Schideman, Ph.D., P.E.
• Dr. Yuanhui Zhang, Ph.D.
• Dr. Michael Plewa
• Peng Zhang
Illinois Sustainable Technology Center
Agricultural & Biological Engineering
Crop Science
Agricultural & Biological Engineering
• Funding: United States Department of Agriculture (USDA)/NIFA/Grant 11332987
41
42
Antibiotics
(FDA, 2009; Mellon M, 2001)
Antibiotics resistant bacteria develop from exposure to low-levels of antibiotics
& life threatening infections (Wise et al., 1998: Schuh et al., 2011)
30 ~ 90% drugs are excreted in urine & feces (Sarmah et al., 2006, Berge et al., 2006)
Spending for antibiotics infections was increased 10 times from 1998 to 2009 (Infectious Disease Society of America)
80%
Antibiotics usage for livestock
1834 tons
14,266 tons
INTRODUCTION
43
Estrogenic compounds
Major source: farm animals & humans (Shore et al., 1993; Raman et al., 2004)
Annual excretion from farm animal: 41 tons in the USA (Lange et al., 2002)
Commonly detected compounds: estrone (E1) & 17b-estradiol (E2) (Nichols et al., 1997)
Adverse effects to reproductive system with E2 (10~ ng/L) (Routledge et al., 1998; Schuh et al., 2011)
Reduced reproductive abilities & Feminization of aquatic species
o Male fish feminization
o Antibiotics in the drinking water
INTRODUCTION
44
MATERIALS & METHODSDetailed Analytical methods: Sample prep
Flow diagram of the sample preparation method for the analysis of estrogenic hormones by ELISA and GC/MS
44