Transport of Chemical Pollutants

1
??? ?????????? Transport of Chemical Pollutants
2
? ??
??? ?????????? ??? ????? ??? ?????????? ???
??????????
3
? ??
??? ??????????
???? ????????????????????
????-?? ?????? ????-??
4
? ????
??(Transformation) ??? (Transport)
????????(?????????),?????,????????????????????? ?
???????????????????????(?????)?
?????????????????????????? ?????????????????????
?? ?????????????????????? ?
5
? ????????????????????
Transformation of Sulfur Oxides in Air and
Pollution of Sulfuric Acid Aerosol
6
? ????????????????????
(2) SO2??????
SO2?HO???
7
? ????????????????????
SO2?????????
CH3CHOO SO2 ? CH3CHO SO3 HO2 SO2 ? HO
SO3 CH3O2 SO2 ? CH3O SO3 CH3C(O)O2 SO2 ?
CH3C(O)O SO3
???????
8
? ????????????????????
3. ???????
???????????,????????????????????????SO2???????SO2?
??????????????????????
9
? ????????????????????
??????????????
? ? ???

???? ? ? ????(1873?),???????
????(1946?),??????? ? ? ? ????SO2?????
??????Nox?O3?PAN???? ? ?
?
???????? ???? ?
? ?
??? ?
? ?(4???)
?(24???) ? ?
?
? ? ?
?
? ????
?
? ????
??????
?? ? ? ?????????,
?????????????? O3????
?????????
????????,?????????   ????????,1993?
10
? ????-??
1. ??????????????????
?????
????
????
????
??
??
????
?????
??
??
?? (????????)
????
????
11
? ????-??
2. ????????
(1) ????????
?????????????,????????????? ?????,?????????????,
??-??????,??????????????
Me(OH)n (s) ? Men nOH-
Ksp MenOH-n Men Ksp/OH-n
KspHn/Kwn -lgMen -lgKsp - nlgH
nlgKw pC pKsp npKw npH
12
? ????-??
????????????????pH????
13
? ????-??
???????????,?????????
14
? ????-??
pH
PbO????(James F. Pankow, Aquatic Chemistry
Concepts, 1991)
15
? ????-??
(2) ???
H2S ? H HS- , K1 8.9 10-8 HS- ? H S2- ,
K2 1.3 10-15 H2S ? 2H S2-
????????????????????????,????????S2-,?????????????
?????
16
? ??????
1. ????
??????????????????????????????????????????????????
??,????????
????,???????????,??????????????????????? ????????
????????,??????????????
17
? ??????
?????????OH-?Cl-?CO32-?HCO3-?F-?S2-?? ??????????
?????????????,????????????????????????EDTA???????
????????????????????????
(1) ???????????
???????????????????????????????,??????????
?????? ??????????(???????)???????(??????
)???????????????????
18
? ??????
???K1,K2????????(???????),?ß1?ß2????????
19
? ??????
2. ?????????????
20
? ??????
21
? ??????
Cd2
1.0 0.8 0.6 0.4 0.2 0.0
Cd(OH)42-
??
Cd(OH)2
Cd(OH)3-
CdOH
lgOH-
-10 -8 -6 -4 -2 0
pH
4 6 8 10 12 14
Cd2 - OH- ???????pH?????(????,1987)
22
? ????-??
1. ??-??????
??????,????????? ???????????????????????,????
?????,????????????????-????,??????
??????????????? ?????????????O2?SO42-?NO3-?PO4
3-??Fe3?Mn4?Cu2?Zn2????????????????Cl-?Br-?F
-?N2?NH3?NO2-?H2S?CH4?? ????????????,???????????
??
23
? ????-??
2. ??-?????????
(1) ???????????
?????? ???? pH -lg(aH) aH____
???????????,?????????? ??????? ?????????????????
?????, ???pe?pe -lg(ae)
24
? ????-??
pe??????????Stumm?Morgan???,?????? 2H(aq) 2e
? H2 (g) ?H(aq)?1?????1.013105Pa?H2??(?????1)???
?, ?????1.00, pe 0.0?
pe??,??????,???????????
pe????
pe????
pe??, ??????,???????????
25
? ????-??
(2) ??????E?pe???
26
? ????-??
27
? ????-??
3. ????pe
????????????????????? ????????????Fe(III)?Mn(IV)?S
(VI)?,???????????H2O?Fe(II)?Mn(II)?S(-2)?? ???????
?????????,?????????,????????????
???????????????????, ?pe???????????pe??,??????????
??pe??
28
? ????-??
?????????????????, ????????pe???????????pe? ??????
??,??????pe????
29
? ????-??
4. ??????????
?????????Fe(OH)3(S)?Fe2??????
30
? ????-??
31
? ????-??
pe
Fe3?Fe2???????lge pE? (W. Stumm, J. J.
Morgan, 1981)
32
? ??
??? ?????
?????? ??????????? ??????? ?????????? ??????? ????
????????? ??????????????? ??????????????
33
? ??????
??? ????? ?? ??
34
? ??????
4 3 2 1 0 -1 -2 -3 -4
? ?
??-????(UV-Vis) ????(IR) ??????(AAS) ??????(AES)
lge
???? ???? ????
???? ????
120 160 200 240
? (nm)
O2????(R. A. Bailey, 1978)
35
? ??????
????????
?????
?????????,????????,??????????,????????????,???????
???
36
? ??????
????????????????????,???????(Ground
state)??????????? ??????? ??(Promote)????? ????
???????????????????(??????,???????)?
????????????,?????????,??????????????
37
? ??????
??????
??????????????(LCAO),???????????????,?????????? ??
?????????,?????????????
(1) ?????? ????????????,??????? (2) Pauli?????
??????????????????????
38
? ??????
HOMO The Highest Occupied Molecular
Orbital LUMO The Lowest Unoccupied Molecular
Orbital FMO Frontier Molecular Orbital
LUMO
HOMO ???????? LUMO ????????? FAO ??????,????
HOMO
39
? ??????
??????
Absorbance (A?) is the logarithm of the ratio of
the initial intensity (I0) of a beam of radiant
energy to the intensity (I) of the same beam
after passage through a sample at a fixed
wavelength ?. Thus, A? log(I0/I).
The Beer-Lambert law states that the absorbance
of a solution of a given chemical species, at a
fixed wavelength, is proportional to the
thickness of the solution (l), or the light
pathlength, and the concentration of the
absorbing species (C).
A? e?Cl
40
? ??????
Molar absorptivity (e?) is the proportionality
constant in the Beer-Lambert law when the
concentration is given in terms of moles per
liter (i.e. molar concentration). The units of e?
are molar1 cm1. Numerical values of molar
absorptivity depend upon the nature of the
absorbing species.
proportionality prE7pCFE5nAliti
41
? ???????????
1. ?????
??? (Electronically Excited Molecules)??????????,
??????????????????????????????,???????????????,???
?????????????? ??(Promote)????? ????????????????
??????????????(??????,???????)?
hv
42
? ???????????
?? (?) ?(S0) (Triplet state)??????????
?????(S1)???????????????,??????????
?????(S1)?????????????,???????
43
? ???????????
S2
S2
S1
S1
S1
S0
S0
S0
??
???
??????
? S0?S1???????,S0?S2, S3?????????????,S2,
S3???(??10-13 s?10-11 s)???S1?
44
? ???????????
????????????
Electronically excited molecules are one of the
three relative and unstable species that are
encountered in the atmosphere and are strongly
involved with atmospheric chemical processes.
The other two species are atoms or molecular
fragments with unshared electrons, called free
radicals, and ions consisting of
electrically-charged atoms or molecular fragments.
??????????????????????
45
? ???????????
?????????????????
?????,6.626 10-34 (Js)
E hv
????(hz)
1??????
????????167.4 kJ/mol,????????
46
? ???????????
2. ???????
?????????????????????? (1) s?s???s?????s??(s)??
?,??????????? (2) n?s????????n???????s??(s)????
??????,?????,????????
47
? ???????????
???????
(3)p?p,???????p????????p??(p),??????????????????
???,????????? (4) n?p ,?????????n????????p??(p),
????????????????????
48
? ???????????
?? ? max125 nm ?? ? max135 nm ?? ? max183
nm ??? ? max227 nm
??

??

??
??


p?p ??
n?p ??
s?s ??
n?s ??
??? max280 nm
49
? ???????????
??????
? ?????????????,??????
? ????????????????????(??????????????)?
? ?????????????????
????????? ???? ???? ???? ????????
?????
50
? ???????????
?
3. ?????
?
????(VC)(Vibrational Cascade)
VC
IC
VC
S2
???????????????,????????????????,?????????????????
??? ???????(S1)????
ISC
hv
S1
hv
hvf
VC
ISC
hvf
?
?
?
?
Triplet state
S0
Singlet state
51
? ???????????
?
????(IC)(Internal Conversion)
?
VC
IC
????????????????????????????????????,?????????????
??????
VC
S2
ISC
hv
S1
hv
hvf
VC
ISC
hvf
?
?
?
?
Triplet state
S0
Singlet state
52
? ???????????
?
????(Fluorescene, hvf)
?
VC
S1???????????????S0??,???????????????????????(10-9
s),?????,????????,???????????? ??????????????????
?
IC
VC
S2
ISC
hv
S1
hv
hvf
VC
ISC
hvf
?
?
?
?
Triplet state
S0
Singlet state
53
? ???????????
?
???? (ISC) (Intersystem Crossing)
?
VC
????????????????????????,?????????????????S1??????
????????? ????????????,????????????????
IC
VC
S2
ISC
hv
S1
hv
hvf
VC
ISC
hvf
?
?
?
?
Triplet state
S0
Singlet state
54
? ???????????
?
????(Phosphorescence)
?
??T1???????S0??,?????????T1????????????????S0??,??
???????????????????????????,?????10-3 s?10-1
s,????T1???????S1??????????
VC
IC
VC
S2
ISC
hv
S1
hv
hvf
VC
ISC
T1
hvf
?
?
?
?
Triplet state
S0
Singlet state
55
? ???????????
?????????????,???????,??????????????????,?????????
??T1????????T1???S0??????,???????
Triplet state
Singlet state
56
? ???????????
????????
??????????????????????,??????????? ???????????????
????,??????????????
D A ? D A
???????????,D??????????,????????????????????,????
????????????????
???????????????????????
57
? ???????
?
???????????????(????)
58
? ???????
?????
(Photochemical Reactions) ?????????????????
?????
59
? ???????
1. ?????
(1) ??????E2?????????,??????,???????????????
????????????
60
? ???????
(2) ????????E2???????,??????????? ???? ??? gt
??????????(?10-15 s)????????(?10-12
s)? ????,????,???????????
61
? ???????
(3) ?????,????????,?????????????,??????????????,?
??????,??s?s??,???
??????????????????????????,?????????????
???????????????,??????????????????????
??????????????????????????????(Photolysis,
Photodegradation)
62
? ???????
???? Direct photolysis is the direct absorption
of light by a chemical followed by a reaction
which transforms the parent chemical into one or
more products. ?????????????????? A hv ?
A ? B C
???? (Indirect Photolysis, Sensitized
Photolysis, Sensitizer) ??????????????
(??????????) ,???????????????????? A B ? A
B B ? C D ??????
63
? ???????
?? (Photolysis, Photodegradation)
?????????????????????????????????????? ?????????
?????????????,?????????????????????????
64
? ???????
?????????? ?????????????????????
?????????? ??????????????????????
65
? ???????
2. ???????
????
? ???????
??????230330 nm????,???????????
????
???????O-O?????????R'-NN-R??C-N??????????????R'-N
N-R???????????N2,???????R????
66
? ???????
? ???????
???????????????????
67
? ???????
?????????????,????????? ?

Norrish II?????
68
? ???????
? ?????
??????
69
? ???????
? ??????
?????????????????????,????????????????????a
?,??????????,?
70
? ???????
? ??????
??????(??????????),a,ß-???????????????T1?
Photochemical synthesis of OCDD from
pentachlorophenol (PCP) in atmospheric condensed
water is the most significant source of OCDD to
the environment.
Environ. Sci. Technol. 2000, 34(14) 2879-2886
71
? ???????
Octachlorodibenzo-p-dioxin
PCP
(OCDD)
Polychlorinated dibenzo-p-dioxin
(PCDD) Polychlorinated dibenzofuran (PCDF), PCB,
biphenyl, diphenyl
mono-, di-, tri-, tetra-, penta- hexa-, hepta-,
octa-, octanol
72
? ???????
????? ???? ???? ???? ???? ????????
?????
??(???)?????? ?????? ?????? ???(Hydrogen-atom
abstraction) ????
?????
?????
?????
73
? ??????????
1. ???????
(1) ?????????????,???????????????
????????????????? (2) ?????????????????????
?????????????,??????????????????????????????
?????? ??????
74
? ??????????
????(Quantum Yield)???
?????????????????1?
???????,?????????,?????????,??????????????
??????,???????????????????
75
? ??????????
???
???2HCl hv ? H2 Cl2
??100?HCl??,??100???,??50?????????,30?????
??,20?????,???????????H??????????HCl?????????????
????HCl??????H2?????????

76
? ??????????
?????????? CH3COCH3 hv ? CO 2CH3
??CO????????1,????????????,???????????????
CO????????????,CO????????????????????CO?????F
fCO 1?
NO2???????? NO2 hv ?
NO O ?????NO????????
????,????????NO2??????
-dNO2/dt
dNO/dt
fNO
Ia
Ia
77
? ??????????
???????????????????NO2??????O2??,?????????
?O2????? O O2 ? O3 O3 NO ? O2 NO2
?????,?????????NO?????O3???NO2?????????,????NO????
?F??????????,? F lt fNO ???????NO2,?????O??NO2???
???? NO2 O ? NO O2
???????????,???????? F 2fNO
78
? ??????????
????(Quantum Yields)????????????
??30.6 ?,????435.8 nm??????,????????????,???I1.4
10-3 J/s,?????80.1????????1105 s??,Br2??0.075
mmol,?????????(??)?
79
? ??????????
80
? ??????????
2. ????
??????????,???????????????????(pseudo-)????????
The decrease of selected PAHs in sunlight
irradiation and dark control experiments. Ct is
the concentration of each PAH at time t and C0 is
the initial concentration.
81
? ??????????
The direct photolysis rate constant of an organic
chemical in water, k, can be expressed as
where l is the average cell path length, ? is the
wavelength, F?is the average reaction quantum
yield at wavelength ?, e? is the molar extinction
coefficient, I? is the incident light
intensity. Therefore, the direct photolysis rate
constants are dependent on both internal factors
(F? and e?) which are governed by molecular
structure, and environmental factors (l and I? ).
82
? ??????????
???????????(???????)
?????? ??????
???????????????????????????????
?? ??
????????????????????
83
? ??????????
3. ??????????
(1) ?????????
? ??????????
????????????????????????,?????????,?????lt295
nm???,???????? ????,?????????????????????,????????
??????????????????????????
84
? ??????????
2.5
6000 K??????
???? ??????
2.0
?????,???????
1.5
????/Wm-2nm-1
1.0
???????????????????????
0.5
0
0 200 400 600 800 1000
1600 2000 2600
3000
??/nm
??????
85
? ??????????

• ????

????????????????,UV-B?UV-A????UV-B????????????????
?????????????????,?????????????????,????????
? ????
?????????????????,????????????????????????????????
,???????????,UV-B??50???????????????,??????,?????
?????,??????????
86
? ??????????
(2) ??????????
???????????????????????????
???????????h,??????D,?????????????????
????????
87
? ??????????
?????????,????????????????????????,???????
,???????????48? ????,???????????????
2h?????????????????????,?????????????????
??????(n 1.34)??,ls
1.20D??????????????,ls 1.19D????????????????,???
?????????,?????????????
88
? ??????????
(3) ???????????
? ?????????????,???????????????????????????,??????
??????? ? ????,???????????????????????????????????
??????????
? ??????,?????????????????,?????????
89
? ??????????
?????????a?????????,???????????,???????????-????,?
???,????????????
???????????????????????????,????,????????????,????
???,?????
90
? ??????????
(4) ????????????
(Equations Describing Direct Photolysis Rates)
????????? Only light that is absorbed can
effect chemical change in a system.
91
? ??????????
??????????I?????Lambert????? ?
a? ---??????????(light absorption
coefficient) l---?? (pathlength of the
light) Io?---?????????? (incident light
intensity)
92
? ??????????
?????????????,??????,???????D,?????????????(Ia?)?
Id?---?????????? Is? ---?????????? ld---????????
?? ls---????????
direct radiation sky radiation pathlength
93
? ??????????
???????P???,??????????
e? ------ the molar extinction coefficient of the
pollutant P ------ concentration of a
pollutant
??,??????????(fraction)?
Since pollutant concentrations in water are
usually very low,
94
? ??????????
Thus, the average rate of light absorption
by a pollutant may be expressed as
where
,
j ???????(j6.02 1023),??j???,??????????????????
??,P????mol/L,?????????/cm2s?
95
? ??????????
The equation of ka? simplifies under two
circumstances ? If a?ld and a?ls are both
greater than 2, then essentially all the sunlight
responsible for photolysis is absorbed by the
system and the expression for ka? becomes
96
? ??????????
? If a?ld and a?ls are both less than 0.02, then
ka? becomes independent of a? and can be
approximately expressed as
Very little light (lt5) is absorbed by the system.
97
? ??????????
98
? ??????????
The average photolysis rate is also
proportional to the quantum yield for reaction,
F.
The quantum yield for reaction of complex
molecules in solution is usually not
wavelength-dependent.
99
? ??????????
????????????????????????,?
??????????????,?????????????????,??????????
?????????????
100
? ??????????
??
??
????????????
101
? ???????
1. ??? (Photocatalysis)
??????????????,????????(??)?????????????,??????,?
?????/???????,???????
102
? ???????
??(Valence Band)?????????????????,????????????? ?
?(Conduction Band)????????????????,?????????????
?????????????????????(Eg)?
2. ??? (Photocatalysis)??
?????????????,????????
Reduction
Energy
Acceptor-
Conduction Band
-
Acceptor
hv
Eg
Valence Band
Donor

Oxidation
Donor
103
? ???????
Semiconductors (e.g., TiO2, ZnO, Fe2O3,
CdS and ZnS) can act as sensitizers for
light-induced redox processes due to their
electronic structure which is characterized by a
filled valence band and an empty conduction band.
Absorption of a photon with an energy greater
than the bandgap energy lead to the formation of
an electron/hole pair.
Energy
Reduction
Acceptor-
Conduction Band
-
Acceptor
hv
Eg
Valence Band
Donor

Donor
Oxidation
104
? ???????
???????????3 eV??,?????????????????????,??????????
???????(e-)???(h)?????????,????????? ?????,??????
?????????,??-????????????????????????????????
1 eV 1.6 10-19 J
105
? ???????
TiO2 hv (gt Eg) ? e- h (1) e-
h ? TiO2 ????? (2) h H2O ? OH
H (3) e- O2? O2- ? HO2
(4) 2HO2 ? O2 H2O2 (5) H2O2 O2- ?
OH OH- O2 (6) H2O2 hv ? 2OH
(7) h OH- ? OH (8)
106
? ???????
????????
(1) ???????????? (2) ?????????????????????
?????? (3) ?????????????????????
???????????????????????
107
? ???????
? ????????????,????????????? ? ????????? ?
???????????????? ??????O2????,???????,????????????
?????,????????TiO2????????????TiO2?200-900
nm?????????,????TiO2?200-400 nm??????????
108
? ?????????????
1. ?????????????
4 3 2 1 0 -1 -2 -3 -4
(1) ???????
???????493.8 kJ/mol,????240nm??????????O2????
loge
?lt240 nm
O2 hv O O
120 160 200 240
? (nm)
O2????
109
? ?????????????
N2?????,?939.4kJ/mol,??????127nm?
?????? ? ltlt 120 nm
N2 hv
N N
(2) ??????
??1000 km????,????
O O2 M
O3 M
????1180 nm?????????,?????290
nm????,?????????????????
? lt 290 nm
O3 hv O O2
110
? ?????????????
2 1 0 -1 -2
Absorption spectrum of O3
lge
300 400 500 600
700
?(nm)
O3???? (R. A. Bailey, 1978)
111
? ?????????????
80 60 40 20
e
(mPa-1 cm-1)
350 400 450
?(nm)
NO2????(R. A. Bailey, 1978)
112
? ?????????????
(3) NO2????
NO2????300.5 kJ/mol,?????????????,?290-410
nm????
???????????O3??????
113
? ?????????????
(4) ??????????
????
????
????
????
114
? ?????????????
(5) SO2????
SO2????545.1 kJ/mol?
(6) ?????
????
H-CHO????356.5 kJ/mol?
????
115
? ?????????????
?????,???????
????????HO2????????
Troposphere, Stratosphere
116
? ?????????????
(7) ???????
halogenated hydrocarbons chlorinated brominated fl
uorinated 5flu()Erineit iodized,
5aiEdaiz iodizated, 5aiEdaiz
???????
??
???C-X???? ???????,????????? ??????????
117
? ?????????????
2. ?????
Photochemical Smog
(1) ????
?????????????????????,????????????????????
?,????????????????????????????,???????? ????????
O3???PAN(??????? )?H2O2 ?????
?????(1940?)??????????????????????????
118
? ?????????????
??????
(1) ???????????? (2) ?????? (3) ??????
????
(2) ????

1. ?????????,????,?????????
2. ????????

119
? ?????????????
????
?????
?
NO2
(mL/m3)
NO
O3
000 400 800 1200 1600
2000
??
??????????(S. E. Manahan, 1984)
120
? ?????????????
??-Nox-????????????????????(Pitts, 1975)
121
? ?????????????
(3) ???????
? NO2?????O3???
122
? ?????????????

• ?????(????)????????????HO, HO2, RO2?

123
? ?????????????
? ???????????????NO?NO2???
124
? ?????????????
????
???????
????
125
? ?????????????
HO??????
?????
?????
126
? ?????????????

1. PAN?????O2????
2. ??????????
3. ??????????????

PAN????????
127
? ???????????????
1. ????
????ks(d-1)????t1/2(d)???????,??40,24 h???,????
128
? ???????????????
129
? ???????????????
130
? ???????????????
131
? ???????????????
?????(a) 3,4-?????(b) ??????????(Brezonik, 1994)
132
? ???????????????
???????????,?????????????????????,?NO2-?????,?????
?? NO2- hv ? NO HO ??????????NO2-?????10? ?
??????,???????????????????,?? Fe(III)-OH??? hv
? Fe(II) HO Fe(III)-????? hv ? Fe(II)
CO2 ??,NO2- ?Fe(III)-OH???????????????????HO?????
,????????????
133
? ???????????????
2. ????
???????,????????????,????????? ??????????? gt
250 nm??,???????????????????,??????µmol/L?H2O2?,??
??????????????????????H2O2?????????
???????????? DOM?????
134
? ???????????????
3. ????
?????UV-B (280-320 nm) ??????????????
????????????????,??,pH gt 8.0?,???(triclosan,?????
?????)??????2,8-?????????(2,8-DCDD),??????3.010-2
(Boreen??, 2003)
135
? ??????????????
1. ??????
2. ????
3. ???????
136
? ??????????????
Sunlight
Simulated Sunlight
Atmos. Environ. 2005, 394583-4591. Environ.
Pollut., 2003, 123(1) 39-45. Sci. Total
Environ., 2004,322(1-3) 231-241. Chemosphere,
2003, 50(9) 1217-1225. SAR QSAR Environ. Res.,
2004, 18(4) 265-277.
137
? ??????????????
Comparison of photolysis half-lives in natural
water with these on the surfaces of pine needles,
spruce needles and fly ash for selected PAHs
138
? ??
??? ??????????
?????? ?????? ??????
139
? ??????
1. ???? (Acid-base Dissociation)??
?(HA)?????,?(B)?????,??????
HA ? A- H H B ? BH ???HA B ? BH A-
A-??HA????,BH??B?????????????
??????????????????? ????????????????
140
? ??????
???pH??,???????????????aa?
?????????pH???? ,pH pKa?,??????????,?HA
A-,BH B.
141
? ??????
????????????????pH???????????(Schwarzenbach?,2004)

142
? ??????
2. ???
????????????????????4-???????????,1,2-?????????
???,??????pH??????????????? ????????????????,????
???????????????,?pH??????????????????????,??pH????
???
143
? ??????
2. ???
The isoelectric point (pI) is the pH at which a
molecule or surface carries no net electrical
charge. In order to have a sharp isoelectric
point, a molecule (or surface) must be
amphoteric, meaning it must have both acidic and
basic functional groups. Proteins and amino acids
are common molecules that meet this requirement.
For an amino acid with only one amine and one
carboxyl group, the pI can be calculated from the
pKas of this molecule.
144
? ??????
?????????????????????????,???????X-????OH-
????,????????
??????????????????????????????????????????
???????????
145
? ??????
146
? ??????
??????????????????,???RX??????????
??,KT????????,??????pH???????????????.
147
? ??????
KT?????????????????????????????????????????????,?
KH ??????????? K0???????? KOH
?????????? KHA ??????????? KB
??????????? HA ?????? B ??????
148
? ??????
149
? ??????
1. ????????????
(1) ?????????HO?????????????????????????????O3??
?????
(2) ????????HO?HO2??????(R)??????(RO)????????
(RO2)??????(RCO)
????HO???????7105?/cm3,?????????????20,???????
???????? HO????????????,??????,??????????
150
? ??????
(3) HO?????(Main Sources of HO)
?????,HO??????????????????????O3??????????290
nm????,???????,?????????290 nm????
O3 hv (290 400 nm) ? O O2 O H2O ? 2HO
?????,???????????????HO??????
HNO2 hv ? HO NO H2O2 hv ? 2HO
151
? ??????
2. ???????
(1) ?????(1O2)?????????(O2-)????????(RO2)??????(
RO)??????(HO)
(2) 1O2????????(Photochemical Processes of 1O2
Generation)
1O2??????????????,???????????(6 µs),?????10-14
10-15 mg/L??????????????????(?S??)??????????,?????
?????,????????1O2?????,S?????????,???????????????
152
? ??????
1O2????????????????????????,?????????????????1
10 h????
153
? ??????
(3) O2-????????(Photochemical Processes of O2-
Generation )
???????O2?????????????????????????Fe(III)?Cu(II)?
????????????,?????O2- ?
(4) H2O2?HO
DOM?????????????????,????????????????O2-,O2-??????
????H2O2
HNO2 hv ? HO NO H2O2 hv ? 2HO
154
? ??
??? ??????????
?????? ??????????????? ????????????????
155
? ??????
????
Biodegradation is the process by which organic
substances are broken down by living organisms.
The term is often used in relation to ecology,
waste management, environmental remediation
(bioremediation) and to plastic materials, due to
their long life span. Organic material can be
degraded aerobically, with oxygen, or
anaerobically, without oxygen. A term related to
biodegradation is biomineralisation, in which
organic matter is converted into
minerals. Biodegradable matter is generally
organic material such as plant and animal matter
and other substances originating from living
organisms.
156
? ??????
? ???? (Growth metabolism)
?????????????????,????????????????????????????????
???????????????????????????
???Monod???????????????,?????????
C???????? B??????? Yd?????????????? K
s??
157
? ??????
?CltltKs?,Monod???????????????,?
Monod?????????????????????????,???????????????????
?????
?????????????????????????????????????????????????
???????????????,Y??????????
158
? ??????
? ???
???????????????????????????,??????????????????????
??????,?????????,?????????? ????????????????????
??????????????????
159
? ??????
Cometabolism is defined as the simultaneous
metabolism of two compounds, in which the
degradation of the second compound (the secondary
substrate) depends on the presence of the first
compound (the primary substrate). For example, in
the process of degrading methane, some bacteria
can degrade hazardous chlorinated solvents that
they would otherwise be unable to attack.
???
160
? ???????????????
??? ??? ??? ??? ???
?????
?????
????????(S.E. Manahan, 1984)
161
? ????????????????
???????
? ?????? ?????? ????? ????
Microbial metabolism is the means by which a
microbe obtains the energy and nutrients (e.g.
carbon) it needs to live and reproduce. Microbes
use many different types of metabolic strategies
and species can often be differentiated from each
other based on metabolic characteristics. The
specific metabolic properties of a microbe are
the major factors in determining that microbes
ecological niche, and often allow for that
microbe to be useful in industrial processes or
responsible for biogeochemical cycles.
162
? ????
1. ????????????????????????? 2.
???????????????? 3. ??????????????????? 4.
????????? ???????? 5. ????????????? 6.
????????????? 7. ???????????
163
? ????
8. ?????????????????????? 6. ?????????? 7.
???????????????? 8. ????????????? 9.
?????????????? 10. ???????????? 11.
???????????????????? 12. ?????