What’s missing? Reactions/degradation Air Water Octanol A gas is a gas is a gas T, P Fresh, salt, ground, pore T, salinity, cosolvents NOM, biological.

W et (rain , snow )D eposition

G as

P artic les/aerosols

D epos ition to te rrestria l su rfaces

D ry pa rtic leD epos ition

A ir/w a te r/snow G as exchange

D irec t depos ition to w a te r/snow

S now m e lt& runo ff

D isso lved phase

P artic le bound

P artic le sedim en ta tion

S ed im en t bu ria l

P hytop lankton -inve rteb ra tes-fo rage fish

Aquatic food w ebs

M arine m am m alsP iscivorous fish

W ate rfow l,sea b irds

Terrestrial food webs

L ichen - ca ribou

P lan ts - ca ttle (m ilk, m ea t)

Stra tosphere - ozone layer dep letion

Troposphere - increased U V solar rad iation

CFC , CO 2 , CH 4 G loba l warm ing

Relatively long atm osphere life tim esCO 2 , CFC , CH 4 , P O Ps, m ercury, C l 4 ,C l5 P CDD /FsS PM 2.5

Relatively short atm ospheric life tim esS O x, NO x, CO , VO C s, HC FCs, h igh M W P CD D/Fs, S PM 10, heavy m eta ls

V O Cs, N O xO zone

reac tions w ithH O rad ica l

S O 2 , NO xA cid ic p rec ip ita tion

H 2O

Anthropogenic Sources

N atu ra l S ources

H um ans

H um ans

123

A quatic -Terres tria l-A tmospheric E c osys tem L inkages to Chemic al Cyc les

S .J . E isenreic h (M odified from D. M uir, 1997)

What’s missing? Reactions/degradation

Air

Water

Octanol

A gas is a gas is a gasT, P

Fresh, salt, ground, poreT, salinity, cosolvents

NOM, biological lipids, other solvents T, chemical composition

Pure Phase(l) or (s)

Ideal behavior

PoL

Csatw

Csato

KH = PoL/Csat

w

KoaKH

Kow = Csato/Csat

w

Kow

Koa = Csato/Po

L

Goals of this course

• To give you the tools necessary to evaluate the fate of organic chemicals in the environment in both a qualitative and quantitative way

• To develop your “chemical intuition”

Chemical intuition means that by looking at a chemical’s structure you

can guess something about its:

• Henry’s Law constant

• Kow

• Aqueous solubility• Reactivity

These (few) properties will determine the chemical’s ultimate fate

malathion

phenol

atrazine

CCl4 carbon tetrachloride

Tetrachlorobiphenyl (a PCB)

Estimation Techniques• These important parameters can be estimated

(with varying degrees of success) from LFERs or bond-contribution methods (i.e. from the compound’s structure):

• Henry’s Law constant• Kow

• Aqueous solubility• Reactivity

• The wildcard is toxicity—difficult to estimate simply from a compound’s structure.

The whole world can be seen as a war between

thermodynamics and kinetics• In the first part of this course, we will concentrate

on thermodynamics, i.e. equilibrium– Estimations of Kaw, Kow, solubility, etc, which determine

where a compound will ultimately end up.

• In the second part we will look at kinetics, i.e. the rate at which a chemical is transferred from one environmental compartment to another (or the rate at which it is transformed) – Air-water exchange, box models

Expect familiarity with:• Chemical structures, bonding

• Saturated, unsaturated, aromatic• Oxidation states• Polarity, hydrogen bonding• Functional groups containing O, S, P, N• Heterocycles• Electronegativity• If these terms aren’t familiar, review Chapter 2.

• Basic thermodynamics

H, S, G

Resources available to you:

• Your book: it’s marvelous! (check out the appendixes!)

• However, notation can be difficult

• Online resourceshttp://www.chemfinder.com/

http://webbook.nist.gov/

http://www.syrres.com/what-we-do/free-demos.aspx

http://www.epa.gov/oppt/exposure/pubs/episuitedl.htm

www.wikipedia.com

• There are more than 70,000 synthetic chemicals that are in daily use:– solvents– components of detergents– dyes and varnishes– additives in plastics and textiles– chemicals used for construction– antifouling agents– herbicides, insecticides,fungicides

Why the interest?

Classes of compounds

• BTEX

• PAHs, including methylated PAHs

• Halogenated C1 and C2 compounds

• PCBs

• Chlorinated pesticides

• Brominated flame retardants

• Formed from small ethylene radicals “building blocks” produced when carbon based fuels are burned

• Sources are all types of burning

PAHs

Sources of PAH in New Brunswick

Other20%

Gasoline Motor Vehicles6.7%

Diesel Motor Vehicles5.7%

Natural Gas24%

Uncombusted Petroleum/Evaporative Emissions

18%

Surface-Air Volatilization19%

Oil4.7%

(Gigliotti et al, 2003)

Some PAH structures

anthracene

phenanthrene

fluoranthenenaphthalene

benz(a)anthracene

benzo(a)pyrene [BaP]

• Naphthalene, phenanthrene and anthracene are found in the gas phase

• pyrene and fluoranthene are in both the gas and particle phase

• BaA and BaP are mostly on the particles, Why???

PAHs

• Metabolized to epoxides which are carcinogenic; O PAH

• are indirect acting mutagens in bacterial mutagenicity tests (Ames-TA98+s9)

• methyl PAHs are often more biologically active than PAHs

PAHs

• used as coolants - insulation fluids in transformers, capacitors , plasticizers, additives to epoxy paints

• are thermally stable and biologically stable

• can exist in the gas and particle phases

• Banned in the early 1970’s but still a big problem

Polychlorinated biphenyls (PCBs)

Local PCB impacts

• GE ordered to spent approximately $450 million to dredge portions of the upper Hudson

• The Federal courts have ordered that a TMDL for PCBs must be established for the Delaware River

• EPA Water quality criteria: 44 pg/L• NY state Water quality criteria: 1 pg/L• Typical levels in these two rivers:

1,000-10,000 pg/L

What else is out there?

When the World Trade Center was destroyed USEPA and NYSDEC investigated its impact on water quality in New York Harbor

Simon Litten, NYSDEC

The WTC contained about 1 gallon of PCB in the transformers. Pyrolysis of this material would form chlorinated dioxins and furans.

Work performed by the NYSDOH in 1981showed that pyrolysis of PCB containing transformed fluid also produces chlorinated biphenylenes.

A modern office building is expected to contain PBDEs. Pyrolysis of PBDEs is expected to produce brominated dioxins and furans.

PBDD/Fs released into the environment are expected to undergo reactions where chlorines replace bromines. There 984 polyhalogenated (Br and Cl) dioxins/furans.

Tetra- and Pentachlorobiphenylenes

Tetra > pentaPre-dated 9/11 in sedimentsVery little is known about toxicity

sample tetra penta unitsRector St., 9/14 5500 1010 pg/LRector St., 9/20 14 <0.1 pg/LNC Sludge, 9/19 28 4.3 ng/kgNC Sludge, 9/25 14 1.1 ng/kgWTC N 1.4 <0.1 pg/LWTC S 1.6 <0.1 pg/LWTC W 0.26 <0.1 pg/LWTC South St 0.2 <0.1 pg/LWTC GW Bridge <0.1 <0.1 pg/LArthur Kill Sediment, 1998 57 15 ng/kg

PBDEsOffice buildings contain brominated flame retardants in computers, furnishings, and upholstery. Little is known about toxicity and background concentrations of these chemicals.

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

1-Mono 2-Di 3-Tri 4-Tetra 5-Penta 6-Hexa 7-Hepta 9-Nona 10-Deca

rela

tiv

e a

bu

nd

an

ce

590,000 ng/L, 9/14/01

220 ng/L, 9/20/01

Rector St. run-off contained high levels of deca-PBDE on 9/14