Mass spectrometric analysis of malodorous air pollutants from sewage plants

Journal of Mass Spectrometry and Ion Physics, 48 (1983) 291-294 Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

In terna tional

MASS

SPECTROMETRIC

A. ZEMAN

and

ANALYSIS

OF MALODOROUS

AIR

POLLUTANTS

FROM

291

SEWAGE

PLANTS

K. KOCH

Chemistry Dept., (West Germany)

German

Armed

Forces

University

Munich,

D-8014

Neubiberg

ABSTRACT Thermal desorption GC*MS in the CI(NH3) mode is a sensitive and-specific method for analyzing malodorous compounds adsorbed on activated carbon used in air purification systems of sewage plants, animal breeding stations etc. With the use of mass spectrometric profiles the air purification process can be evaluated not only with respect to the malodorous and/or toxic substances it is intended to remove but also in recognition of the most abundant substances present, which can control its effectiveness. I NTRODUCTEON Air pollution ter

houses,

etc.,

decomposition bons, are

by malodorous

fatty

formed

is a serious

of carbohydrates acids,

fatty

(see also

ted carbon

filter

particular,

Our recent

GC-MS

have

carbons

usually

present

trometric cation

shown

of trace

hydrocarbons

that

that

in this

piggeries,

By anaerobic

complex

of hydrocar-

N- and S-compounds

of the malodorous

and/or

air using

the air treatment

toxic

slaugh-

and aerobic

mixtures

and especially

To monitor

would

high

components,

allows

and similar

selective

emissions present

activa-

process,

in

an effective

detection,

Recent

from municipal

prevents odour

direct

(ref.51

hidden

have

hydroidentifi-

impact

profile.

identification

of interest

results

sewage

of non odorous

in the electron

by a GC2MS

of compounds

be welcome.

emissions

concentration

of a malodour

concentrations

be solved

on odour the

of the osmogenes

characterization method

Iem might

necessary.

plants,

problem. very

1). Purification

of malodorous

and quantification

thus,

ketones

investigations

(ref.l-4)

and,

aldehydes,

sewage

is needed.

plants

cation

environmental proteins

is often

method

from

and

Table

the removal

analytical

emissions

mode

A mass

spec-

and quantifiin the bulk

shown

that

the

of prob-

by CI(NH3)MS.

METHODS GC-MS

profiles

ted carbon flow port,

rate with

were

samples 10 ml min the

obtained

from -1

normal

air

a Finnigan

purification

, desorption injection

0020-~381/83/000~0000/$03.00

using

0

time port

filters 10 min)

liner

4000

COM GC-MS

were

desorbed

in the glass

using

a device

1983 ElsevierScientific Publishing

system.

Activa-

at 25O'C

(helium

capillary

similar

Company

injection

to the

one

292 described with sed min

in ref.6.

The column

a 50 m x 0.25

mm

glass

I.D.

capillary

coated

OV 101; the

temperature was held during desorption at -lO'C, then increa-1 ; the carrier gas was helium at a flow rate of 1 ml at 2'C min

to 200°C -1 . The GC capillary

mass

was

spectra

as reagent 0.3 torr.

were

gas.

was

recorded

The ammonia

The ion source

combined

directly

with

continually

with

an Incas

flow

rate was

temperature

was

the

adJusted P50°C

ion source.

data

Positive

system,

using

to an ion source

and

the

ionization

CI

ammonia

pressure

energy

of

70 eV.

RESULTS Fig.1 sample wage

shows

the GC*ELMS

of activated

profile

carbon

(RIG) of a thermal

obtained

from

desorbate

a malfunctioning

air

from filter

a 2 mg of a se-

plant.

EI-RIC

T

1000 16:40 7

:F%

Fig. 1. GC'EIMS profile desorption in the GC-MS Detailed peaks

mass

observed

chlorinated dimethyl

are mainly

hydrocarbons

The most

solvent column

spectrometric

sulfides.

tified.

With

extraction

racterize

the usual found

the

easily

aliphatic

in polluted

carbon This

Clearly

and/or

and

and aromatic plus

removal

GC2EIMS

compounds

obtained

the problem

only

The

hydrocarbons

and

some

and

of the

profile .adsorbed

traces

ketones

1) can only

is lengthy

by thermal

outlined.

phthalates

(see Table

procedure

the

toxic

air

carbon

in addition,

osmogenes

on silica. occur.

evidences

EICP method

of activated

the osmogenes

of activated

analysis

characteristic

chromatography

of volatiles

from a sample system.

be found

hydrocarbons and tedious,

can not

are

be used

in the carbon

of idenby

by losses to chafilter,

293 and

thus

its effectivity.

Reports scarce.

on CI(NH3)MS

Ammonia

is mostly

ionize

preferentially

ristic

osmogenes

used

osmogenes

classes

to serve

nitrogen

of biogenic

1. Typical

Table

of different

as a highly

(ref.

in emissions

Table

from

reagent

(ref.51

1) also

sewage

are still

compounds

selective

We reported

compounds. origin

of organic

were

that

gas to

the characte-

preferentially

plants

CH3 ‘51-4 CH3’

G-lH2n+l n=l-l, Aikylthiophene

Is‘lbccoc”H2n+I n= 1,2 Acylthiophene

P

Dimethyl (poly)sulfide

~Tz..~,Rz24kR~Tx~ R3’ Qk L

k

Y

Mono-,di-, trialkylpyrazine

Q

cxv3

Jndole

2-Methyli ndole

Pyridin e

FdMo”rtehY’(Skatole) ionized

in contrast

are observed

and

Fig.

the GC2CI(NH3)MS

2 shows

No peaks tained used

can be used

corresponding

by direct

The

profile

desorption

for qualitative

process

following

to establish

because

questions

intense

(M+H)+

an osmogene

(RIG) of the

to hydrocarbons

thermal

advantageously

purification

Very

to hydrocarbons.

can

and/or

it is a real

specific

sample

be found.

of activated

carbon

from

odour this

what

the components

preferentially

actually

desorption

we now

amount desorbed

of sample

realized (ca.

and thermal

can

the

be

air

of low recovery that

1-2 mg) artifact

this

and artifact

is not a serious

is desorbed. formation

adsorbed

on

adsorbed?

iii) what is the adsorption capacity of the air filter depending ponents under the conditions of air purification employed? possibility

ob-

can be evaluated:

ii)

the

1.

profile,

the filter,

monitoring'of

are the odorous and/or toxic substances to be removed activated carbon and what is their concentration?

Concerning

profile. in Fig.

profile.

1)

are

(M+NH4)+ions

presented

Therefore

quantitative odour

and/or

Also

high

formation problem

boilers

is not observed.

on certain during

if a very like

indole

com-

thermal low can

be

294

CI(NH$-RIC

1000 16:40 Fig.L. GC2CI(NH3)MS

1500

2000 33:20

25:QO profile

from

the

sample

2500 E= 41:40 shown

in Fig.

1

REFERENCES 1 2 3 4 5 6

P. Bartl, A. Schaaff and A. Zeman, gwf-Wasser/Abwasser 120 (1979) 269-274. A. Zeman and H. Hagenguth, APCA 73rd Annual Meeting, Montreal, Canada, June 1980, Paper 80-40.7. 122 (1981) H. Hagenguth, H. Teichmann and A. Zeman, gwf-Wasser/Abwasser 263-269. A. Zeman and K. Koch, APCA 74th Annual Meeting, Philadelphia, USA, June 1981, Paper 81-15.5. A. Zeman and K. Koch, J. Chromatogr., 216 (1981) 199-207. H. Peterson, G.A. Eiceman, L.R. Field and R.A. Sievers, Anal. Chem. 50 (1978) 2152-2154.