No.

Environmental technology: water purification and soil remediation

March, 2013 Toyohisa Fujita, Energy and Environmental course, Graduate school of Engineering, RACE The University of Tokyo, Japan tfujita@sys.t.u-tokyo.ac.jp

1. Water purification Outline of wastewater treatment of old mine drainage in Japan

The University of Tokyo Prof. Toyohisa Fujita tfujita@sys.t.u-tokyo.ac.jp j @ y y jp http://park.itc.u-tokyo.ac.jp/tfujita-lab/

Environmental standard and effluent standard of some metals and pH in Japan (2013)

Amount of waste water and treatment cost of old mine drainage in Japan from 2003 to 2012.
*In case of wastewater related on drinking water. JOGMEC (Japan Oil, Gas and Metals National Corporation) (2013),
http://www.jogmec.go.jp/jogmec_activities/mp_control_metal/technology/index.html

Sulfide minerals

Reaction equations of minerals with water and air

Effect of acid mine drainage

Precipitation

China, F ji province Chi Fujian i Japan, Kitakami river

From AIST, Japan

Matsuo neutralization plant of acid mine drainage, Japan

Some wastewater treatment methods of old mine drainage in Japan

Wastewater treatment types of old mine drainage in Japan

Old mine drainage places in Japan planning the waste water treatment from 2013 to 2022.

As received wastewater; pH 3.7, Cd 0.2, Cu 6.4,

Pollution control plan of old mine drainage in Japan from 2013 to 2022
Oldminetype Mine owner exsistenceMine ownerless Civil engineering works to prevent mine pollution Tunnel, places 29 28 Stockyard, places 49 15 Cover soil, hectare C 83 1 Planting, hectare 70 2 Retaining wall, m 0 1478 Dam, m 154 0 Drainage ditch, m 10,903 4,765 Repair work of facility, places 8 5 Total waste water treatment Old mine drainage place, number 55 24 3 Total waste water amout, million m /year 5.46 1.53 Cd in waste water, t/year 9 0.2 Pb in waste water, t/year 144 1.5 As in waste water, t/year 11 23 Cu in waste water, t/year 194 46 Zn in waste water, t/year 1985 50 Fe in waste water, t/year 3783 2703 Mn in waste water, t/year 1238 51

Pb 0.7, Zn 23, T SO4 590,T. Fe 6, SiO2 70 ppm

Flow sheet to remove cadmium ion from mine effluent using flotation.
Jeyadevan, B. et al. (1999). Treatment of old yoshino mine drainage and removal of cadmium ions: Proc. Global Conf. on Environmental and Metallurgy, GME 99, Beijing, China; The Nonferrous Metals Society of China.

The distribution of arsenic(III) and arsenic(V) species in water in the presence of the iron compound as a function of pH, showing the total adsorbed As (denoted as Total ADS As)
100 90

100 90

T Total Concentration of As , (%)

To Concentration of As , (%) otal

80 70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

80 70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

AsO3

5+

3-

AsO4

3+

3-

Fe(wk)H2AsO3 HAsO3
2-

Fe(wk)HAsO4 Fe(wk)H2AsO4 HAsO4

2-

H3AsO3 H2AsO3 H4AsO3

+ 3-

H3AsO4 Fe(wk)OH-AsO4 Total ADS AsO4

33-

Total ADS AsO3

pH

pH

a. As(III)

b. As(V)

(Input Parameters - As concentration: 2.7 x10-5 mol/L; Fe concentration :1 x10-3 mol/L)

Adsorption isotherm of arsenic species onto FeCl3-based and poly-Fe-based adsorbents (experimental conditions: initial As concentration: 2mg/L, adsorbent dosage: 0.0120 g/L, contact time: 120min, pH of solution 7, and T=25oC).

Cr removal

Equilibrium concentration of arsenic species as a function of contact time (experimental conditions: initial As concentration: 2 mg/L, adsorbent dosage:0.1 g/L, contact time: 10300min, pH of solution 7, and T=25oC)

(a)

(b)

(a) SEM image for pineapple leaves before adsorption, adsorption (b) SEM image for 723 K carbonized pineapple leaves after Cr6+ ion adsorption.
Ponou, J. et al. (2011). Sorption of Cr(VI) anions in aqueous solution using carbonized or dried pineapple Leaves: Chemical Engineering Journal, 172, 906 913.

Effect of contact time on the removal of Cr(VI) anions by 723 K carbonized pineapple leaves (PL723), 623 K carbonized pineapple leaves (PL623) and dried pineapple leaves (PL): initial pH = 2; initial concentration: [Cr(VI)] = 5 mg/L; adsorbent dosage 10 g/L; temperature 293 K.

Distribution of Se(VI) species and the total adsorbed Se (Total ADS Ae) as a fuction of pH.

Effect of pH on removal of selenium (VI) ion by adsorbent of ferric cupric hydroxide powder. (adsorption capacyty, concentration of copper,conditions : adsorption period 2 h, 298K)

(a)---2mm

(b)--100nm

(a) SEM image of surface of natural dolomite (As received ore) (b) SEM image of calcined dolomite surface (Calcined dolomite in 750 oC for 0.5 hour, D750n)
Kuriwada, A. et al. (2012). Boron Removal and Recovery by Adsorbing Effect of Boron on Thermally Treated Dolomite in the Water Containing Boron Ion

Effect of calcination temperature of dolomite on boron adsorption for long term. Adsorbent: Dn; Natural Dolomite, Dc750; Calcined dolomite at 750oC for 30 min. Dc850; Calcined dolomite at 850oC for 30 min., Dc950; Calcined dolomite at 950oC for 30 min., Dc1050;Calcined dolomite at 1050oCfor 30min., Amount of adsorbent; 500mg/25mL, Initial boron concentration, 652mg/L, Particle size ; -75m

Heavy metal concentrations and pH in the as received Ashio acid mine drainage sample as well as the effluent standards in Japan

Wang, L. P. et al. (2013). Investigrating sulfidization with neutralization treatment for selective recovery of copper and zinc over iron from acid mine drainage (AMD): Mineral Engineering, in print

Flow sheet to recover Cu, Zn and Fe in the precipitate generated at each treatment stage.

Water pollution

0.003 0.1

as nitric acid

10

A week acid Strong affinity for many metal ions. Less toxic Fe(CN)64Volatile HCN is very toxic.

Inorganic species [H ][CN ] = 6 x10 Cyanide: HCN in water K =

+ a

[HCN ]

10

Ammonia

and other inorganic pollutants

Ammonia: Exessive levels of ammoniacal nitrogen cause water quality problems. pKa 9.26 problems pKa=9 26 Hydrogen sulfide: H2S is a weak diprotic acid . Affinity for many heavy metals as metallic sulfides.

pKa1 = log
0.8 1 0.03 8 10 2

[HS ][H ] = 6.99

1 +

[H 2 S ]

pKa2 = log

[S ][H ] = 12.92 [HS ]

2 +

Nitrite ion
NO2- occurs in water as an intermediate oxidation state of nitrogen over a relatively narrow pH range. Sulfate

Oxygen, Oxidants and reductants

The degree of oxygen consumption by microbial mediated oxidation of contaminants in water is called the biochemical oxygen demand BOD.
This parameter is commonly measured y determining the quantity of oxygen utilized by suitable aquatic microorganisms during a 5-day period.

ion

SO22- is found in some industrial wastewaters. Sodium sulfide is commonly added to boiler feed waters as an oxygen scavenger: 2SO32- + O2 2SO42- (N2H4 + O2 2H2O + N2(g)) The pKa1 of sulfurous acid is 1.76 and pKa2 is 7.20., sulfite exists as either HSO3- or SO3- in natural water.

Perchlorate ion
ClO4- h emerged as water pollution problem i some areas. has d t ll ti bl in Perchlorate in water is very unreactive, and all common perchlorate salts other than KClO4 are soluble, so it is difficult to remove. EPA standard in drinking water: 1ppb Asbestos

{CH2O} + O2 ----- CO2 + H2O NH4+ + 2O2 H+ + NO3- + H2O 4Fe2+ + O2 + 10H2O 4Fe(OH)3(s) + 8H+ 2SO32- + O2 2SO42-

in water

The addition of oxidizable pollutants to streams produces a typical oxygen sag curve.

Organic pollutants
Sewage

Disposal problem of sewage in ocean

Biosorption

10

11

Phytoremediation
Passive treatment
Organic materials

Calcite Anaerobic wetland

As Adsorption Utilization of wall

Clean water

PRB: Permeable reactive barriers Fern From AIST, Japan

Clay minerals and soils

2. Soil quality and remediation q y
The University of Tokyo Prof. Toyohisa Fujita tfujita@geosys.t.u-tokyo.ac.jp j @g y y jp http://park.itc.u-tokyo.ac.jp/tfujita-lab/
Weathering of silicates

12

Primary mineral weathering

13

Organic matter

Bulk of clay particle

14

Soil Washing

15

16

17

18

2.4mm diameter

Quiz: waste water

1. List functional groups related on the biosorption. y g 2. Why is the ferrous oxidizing bacteria used to clean the acidic mine drainage containing Fe2+ ion. 3. Calcium carbonate and calcium hydroxide are common used to neutralize the acidic drainage. Write the problems to use these alkaline materials.

Quiz: Soil washing g

1. List four groups used in the soil cleaning process. 2. Write three difference cases of contaminated soil.

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