Potential metal pollution in grass and soil samples around brickworks

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ABSTRACT/42 soil samples, chosen from 4 transects around orickworks in the G6ttingen area (W. Germany), were examined for the toxic elements Bi, TI, Cd, Pb ...
Potential Metal Pollution in Grass and Soil Samples around Brickworks

This investigation was undertaken to see whether brickworks are potential emitters of the toxic heavy metals Hg, Cd, TI, Bi, Pb, and Zn. Two methods of determination were used. First, the levels of these toxic elements (except Hg) in plants and soils downwind from the brickworks were compared with the levels of these toxic elements in plants and soils upwind and in control areas. Second, the content of these heavy metals in the raw materials was compared with that in the end product's, and the net loss (calculated on the assumption of no loss of magnesium) was assumed to have been discharged into the atmosphere. The studies were conducted in the vicinity of G6ttingen, a city of 130,000 inhabitants in mid-eastern West Germany, located in a relatively unindustrialized farming area, relatively free of sources that would produce high heavy metal concentrations.

Sampling and Sample Preparation

H.-J. Brumsack G e o c h e m i s c h e s Institut V. M. G o l d s c h m i d t s t r . 1 D--34 GSttingen W. G e r m a n y

ABSTRACT/42 soil samples, chosen from 4 transects around orickworks in the G6ttingen area (W. Germany), were examined for the toxic elements Bi, TI, Cd, Pb, and Zn, as well as Fe, Mn, and ~rganic carbon. In 44 plant samples (grass) taken from the same sites the trace elements Cd, Pb, and Zn and the matrix elements K, Ca, Mg, and Na, were determined. Around brickworks, which are situated in an unfavorable morphological region, small anomalies could be :letected. A comparison with a highly polluted area around a leadzinc smelter shows the relatively low level of pollution of the 36ttingen area. ~y investigating 3 different sets of clay and bricks, the loss of some Jolatile heavy metals in the process of converting clay to brick could oe estimated; the losses are between 17 and 83 percent. Extrapolating this to the entire German Federal Republic, Cd, TI, Bi, and Hg are emitted in the 10-30 (tons per year) range, Pb and Zn n the 500-1000 t/y range. The contamination of the environment ~y these metals from brickworks is about equal to that released 3y the coal as it is burned.

In and around G6ttingen 4 transects across brickworks were chosen for sampling (Fig. 1). Each transect consisted of 10 to 12 sample sites, lying in the main S S W - - N N E wind direction (according to the 10 year median wind rose of the G6ttingen area; personal communication of the G6ttingen meteorological station). transect A B C D

location (size) G6ttingen (city) Parensen (village) Hardegsen (small town) Bilshausen (village)

emitter brickworks brickworks cementworks brickworks

B i [ s h o u s e n ~ . ~ ~z

}I L'~

N

~

motorwQy

~ 9

towns,vi[Ioges

rivers

ot*d

~

g

brickwotks

~ObtfinQen

Figure1. Map of the G6ttingen area (W. Germany) showing the transects and the numbered sample sites. -nvironmental Geology, Vol. 2 pp. 33-41 9 1977 by Springer-Verlag New York Inc.

33

4

H.-J. B r u m s a c k

Sample sites from transect A are,mainly situated in the city and the suburbs of Gfttingen. Some sites of transect C lie in the town center, others on land that is used predominantly for agriculture. Samples of transects B and D are taken from rural areas. It may be important that transect B is situated in a predominantly grain growing area, whereas in transect D field crops (potatoes, turnips) are abundant. A grass and a soil sample (the upper 5 cm) were taken at each site. Where possible, the soil sample was divided into an upper and lower 2.5 cm part. In addition, samples of the clay used in the brickworks, and baked bricks were collected. Grass and soil samples were freeze-dried to constant weight before analysis. Soil samples were homogenized in an agate mortar, grass was pulverized in a modified coffee-mill and to avoid contamination, PVC parts were substituted for metal parts. The clay and the bricks were treated in the same way as the soil samples.

Precision and Accuracy The precision of the method was tested in 10 series of doul runs that were arbitrarily selected from all values. Using t formula recommended by Kaiser and Specker (1956) the folio ing standard deviations were obtained:

Analysis Because of the high organic carbon content, soil samples were digested under pressure in an autoclave by a mixture of perchloric and hydrofluoric acids (Wahler 1964). The acids were evaporated on an electrically heated metal block. The residue was dissolved in dilute hydrochloric acid. In these solutions Fe, Mn, and Zn were determined by a Perkin-Elmer 303 double-beam atomic absorption spectrophotometer by flame. Pb as well as Cd, Tl, and Bi were analyzed by flameless AAS, using a PerkinElmer H G A 70 graphite tube atomizer with background corrector. Before analysis Cd, T1, and Bi were separated and concentrated by a volatilization technique described by Heinrichs and Lange (1973). Organic carbon was determined coulometrically by a Coulomat 7012 (Herrmann and Knake 1973). The clay and brick samples were treated in the same way as the soils. Plant material was decomposed by low temperature ashing (Tracerlab LTA 505). By stirring the sample after 3 hours, the time used for decomposition could be reduced in half (12 hours). The residue (ash) was dissolved in a mixture of 2 ml distilled water and 0.1 ml hydrochloric acid and was rinsed into a teflon liner. Then 0.1 ml hydrofluoric acid and 0.3 ml perchloric acid were added to destroy silicates and remaining organic compounds. After evaporation of the acids the residue was dissolved in diluted hydrochloric acid. For Cd determination 0.05 ml sulfur-

Table 1

ic acid was added instead of perchloric acid. Carbon removed by adding 0.1 ml of hydrogen peroxide (Table 1). The inorganic residue of plant material consist of the ma elements Na, K, Mg, and Ca. These elements were analyzed 20 samples. The mean values in ash were: N a 200 ppm, Mg 0. percent, Ca 0.50 percent, K 2.30 percent. A major source of error in analyzing with the graphite tube produced by high K concentrations in the solutions (pe suppression factor up to 0.5 !), Therefore the weight of~ sample was chosen according to the K concentration, so that: sample solutions had a K concentration of 400 ppm. All standa solutions used for calibration were spiked with the same concentration (matrix assimilation).

Acid Treatment during Decomposition

1St digestion 2nd digestion

Element (soils) S.D. Range Element (plants) S.D. Cd 6% 0.2-3.0 ppm Cd 11% T1 6% 0.1-0.6 ppm Pb 3% Bi 13% 0.05-0.4 ppm Zn 2% For testing the accuracy, two biological standards analyzed: IBS Standard Kale (Bowen) NBS Orchard Leaves (SRM 1571) Standard samples were treated in the same way as the pl; material. Table 2 gives the analytical data obtained by the met~ described above and results from other studies.

Results and Discussion Soils

Fig. 2 shows the range of element concentration and the rn~ value of the 4 transects. For comparison, the mean value of samples, the average of shales, the background value, and( extremely high value from a contaminated area around a le zinc smelter are listed. It is striking, that the mean values of

of Plant Material

HCI

HF

HCiO4

H2SO4

H202

Elements determined

0.1 ml 0.1 ml

0.1 ml 0.1 ml

0.3 ml --

-0.05 ml

-0.1 ml

Pb, Zn, K, Mg, Ca, Na Cd, (Pb), Zn, K

M e t a l P o l l u t i o n in S a m p l e s a r o u n d B r i c k w o r k s

Table 2

35

M e a n V a l u e s of S o m e M a j o r and M i n o r E l e m e n t s in B i o l o g i c a l S t a n d a r d s

Bi ppm

This paper s.d. Bowen (1974) Schramel (1973)

0.03 (5) ---

TI ppm

Cd ppm

0.24 (4) _~0.05 0.15 --

0.97 +0.19 0.80 0.75

0.04 (4) *0.02 ---

0.19 (10) -+0.04 0.11 0.23

(7)

Pb ppm

Zn ppm

3.2 (5) -+0.3 2.65 2.6

32.8 • 33.2 --

(4)

33.6 -+ 1.5 45 44

23.2 -+2.2 25 24

(5)

Na%

Mg %

Ca %

K%

0.24

0.15

4.17

2.34

0.25

0.16

4.09

2.46

0.02

0.56

1.91

1.41

0,008

0.62

2.09

1.47

NBS+ This paper s.d. NBS Certificate Segar and Gilio (1973)

0.03 (3) (0.1) --

(4)

" I n t e r n a t i o n a l Biol. S t a n d a r d , B o w e n , ( S t a n d a r d Kale) + N a t i o n a l B u r e a u of S t a n d a r d s , S t a n d a r d R e f e r e n c e M a t e r i a l 1571 ( O r c h a r d L e a v e s ) ( ) N u m b e r of d e t e r m i n a t i o n s All values referred to dry m a t t e r .

transects A and C are generally higher than those of transects B and D. In particular, Cd shows a wide range of values in transect A, obviously caused by the larger density of population and the correlated larger amount of coal burning. The differences in the Cd and Zn concentration between transects B and D may be caused by different agricultural cultivation as mentioned previously, and especially by different fertilization. As Williams and David (1973) showed, phosphatic fertilizers contain large amounts of Cd and Zn. The Pb and Bi concentrations of soils show little variation and are similar in all transects. The Pb concentration in soils is considerably influenced by motor exhausts. Particular Bi and TI sources are not yet known. A comparison of the heavy metal content of uncontaminated soils and shales may be of interest. Table 3 shows, that the level of concentration for Pb and Zn is about the same. On the other hand Cd, T1, and Bi are enriched in shales by a factor of 2 to 5. Considering the position of soils in the natural cycle of the elements the close contact to the atmosphere, biosphere, and hydrosphere may explain these data. As Peirson and others (1973) and Ruppert (1975) showed, heavy metals are enriched in airborne particles by a factor of 10-100 (normalized according to the A[ content). The soluble components are washed out of the soils by rain and later partly concentrated in shales and partly in seawater. The biosphere is in equilibrium with the soils, hydrosphere, and atmosphere and may be important for the fixation of heavy metals. An indicator for this biogenic fixation is the correlation between the sum of heavy metals and the organic carbon content of soils (Fig. 3). The sum of heavy metals is a number without dimension. Each sample is evaluated according to its position in a frequency distribution diagram (Fig. 4). The num-

bers of the 5 heavy metals investigated here are summed up and give the degree of contamination for each sample. Samples with

o~

A

o

I

,._.z-

B C

'

t

D

L

9 9

.9. . . .ml,~'~ "~1~1 "" ~176176 ~~ Q.I[ samples

Bi

i

o O D

i

o~

u@

'...... '

"1~r kgn~nd contaminated soil L~e(ter) averoge shal*

A B

'

C

"

'

i

D

TI

9 i 9

'

o

B C

''

D

m

v

t

Cd

' i L

9

i

9 i

coy i

A B

C

t

9

J

"" i

Pb

9

i

D I

oar

A

B

~

'

T

C D

062 'obs 61 o12

o:s i

:~

s

~

io

9

, t

t

t

? 9

Zn i i

so 1oo 260 soomoo2~ooppm

F i g u r e 2. Mean values and ranges of heavy metals in soils.

6

H.-J. B r u m s a c k

Table 3

Comparison

of the Heavy Metal Content

Coals (All Values

of Soils and Plants (Dry Matter) with the Average

o f S h a l e s and

in p p m )

A

B

C

D

E

F

G

H

G A

B A

C A

H -D

E D

F

Element Bi TI Cd Pb Zn

0.10 0.20 0.35 20 75

0.28 0.60 1.0 80 300

1.07 1.07 6.83 845 690

--0.24 8 24

---

~ --

1,0 36 100

3.2 145 400

0.35* 0.99* 0.69* 22* 95+

0.16" 0.15* 1.2* 22* 78*

3.5 5.0 2.0 1.1 1.0

2.8 3.0 2.9 4.0 4.0

10.7 5.4 19.5 42.3 9.2

--5.0 2.75 3.25

--4.2 4.5 4.2

--13,~ 18.: 16,7

A B C D

= = = =

background value contaminated soil contaminated soil background value

soil (10) Gbttingen (5) smelter (2) grass (14)

E F G H

= = = =

contaminated grass G6ttingen (5) contaminated grass smelter (2) average shale (59) average coal (15)

*Henrichs 1975 + W e d e p o h l 1969 (

) n u m b e r of samples used for this calculation

the lowest sum concentration were selected to represent the potential background level (see Table 3). In comparison to these background values the soil samples have maximum factors of accumulation of 3 or 4. This is still close to the normal level if one considers the factor of accumulation of 40 found in soil samples around the smelter.

~ c:;d~

Bi ~ o

ppm

,t

Jill

5.0"

Figure4.

~

oI lol

Frequency distribution diagram of heavy metals in 42 s

samples. r L_ o

4.0" 3.0 2.0 00000 ~

1.0

9

09

I

10

i

i

!

!

20

30

40

50

heavy

metals

Figure3, Correlation of heavy metals in soils (expressed as sum concentration) with the organic carbon content.

By separating 25 of the 42 soil samples into an upper an~ lower sample, 2.5 cm in length, it was possible to get an in& tion of the mechanism of fixation. The elements Cd, T1, Bi, Pb are enriched in the upper part. Atmospheric precipitati supplies these fractions of the elements. An enrichment in t upper part was to be expected, especially if one considers t biogenic fixation process and the higher organic carbon cant{ of the upper soil level. In contrast to Cd, T1, Bi, and Pb, Zn enriched in the lower part (see Fig. 5). This phenomenon could explained by the different crystal-chemical behavior of this e merit. Zn shows the greatest tendency to substitute Mg and F in clay minerals, because of similar ionic radii and bonding. grain size effect cannot be excluded to explain the changes in t metal concentrations.

Metal P o l l u t i o n in S a m p l e s a r o u n d B r i c k w o r k s

upper

o.~

..

~

o.,fl .- ,.;/. ~176 }

9

./

""

-

,

..

~176-// o~1/

Bi

0.62 0.~ 0.10 0.{/, 0.i8 0.22 Ct26 ppm lower 2.5 cm

011 0'.2 0'.3 0'.1, 015 (3.6 ppm lower 2.5 cm u

r

upper t 2.5 cmJ

80.

3.0!

60.

2.0"

50.

1.5.

40-

,,01

70. t e

30.

1.0. 0.5'

. ' /

::...E

20.

/.

9

10.

S/" eb ~'o zo 3o ~o s'o ~o ~o .pr. .

0".5 110 115 210.'-;3~0=~-4,~0ppm lower 2.5 cm

i

i

lower 2.5 cm

upper

250. 200' 150. 100. 50.

"

"t"

""

.~3

Zn

10C) 1.50 2(~)0 250 300 ppm lower 2.5 cm

=lgure 5. Correlation of the heavy metal content between the upper and lower 2.5 cm part of 25 soil samples.

37

8

H.-J. B r u m s a c k

o

v

.A. B C

L ,

[]

9 i

D

,

Cd

9

9

,_I_, v O 0 []

t

9

9

,

ov

A

n

,

C

9

,

9

i

D

Pb

i L

9

j

015 i

012

2

A

,

a

L

9 9

LT~

D

,

I0 2'0

Zn

I

C 5

[]

v

0

6.1

mean value and range of a transect mean value all samples background contaminated gross (smetter) average coat

9

5'0 I(50 2(X) 560 10(X)ppm

9

gppm

!it

Zrl

....

. ~ . ~

.~"

/\

Figure 6. Mean values and ranges of Cd Pb, and Zn in plants (all values referred dry matter).

,

I

r

9

gpprn

Figure 7. Frequency distribution diagram of heavy metals in 44 grass san (all values referred to dry matter).

_.~. p~

50

/.

Zn 1~ . . . .

""

~"

'~'""*

cao.,l.___.___.~- " ~

.__.

. . . . .

C

Cd

~

"\.~.

(Isl.~.-1"~.

20

Z00

ppm

z~ ;:o

~

....

A

6O

ppm 4O Pb zo ppm

CA

~3 2

9

401

0"Zl

~T~

8

........

~

.-------'-

"\.

? 10

9 "12 3

transect A

PPm t TI 01 9

' "9/, 6 5

.\

/ ' ~

~.__.~

.

.~'--.

Ram 11 =-.-,*-. Cd o ..............

~.~.

.____-- i

"

Pb , o { ' ~ ' 7

e~.e

TI o~ , ~ g

,q .__ / \ _ . 7 ~ . _ _ . , . / . 25 J

/\ .~-~.~./

P~

_._=

7~;1

.____/.--~.~/'J\__.~

~

~\

t" . . . .

. . . . . . .

__R Bi o, 9 8 01710 2 transect B

3

/, 5 6

Figure 8. Element concentrations in and grass (dry matter) along transec'r C, and D (the location of the potenti polluter is marked by a solid circle)

Metal Pollution in Samples around Brickworks

Plants Fig. 6 shows the range and mean value of each transect, the average of all samples, the background value, the extreme value around a smelter, and the average of coals. It may be of interest to compare the heavy metal content of plants with that of coals (see Table 3). All elements are enriched in coals by a factor of 3 to 5. In the same range, the factors of accumulation are correlated with the degree of coalification. Therefore coals may represent a kind of natural background for these elements. In transect A the maximum enrichment of heavy metals is 4 times the background level. Around the smelter the accumulation is more than 4 times higher (factor 18). Fig. 7 shows the frequency distribution of heavy metals in plants. A correlation between the heavy metal content of plants and soils could not be detected, perhaps because most samples have concentrations close to the background.

Transects Heavy metal concentrations at the 4 transects are shown in Fig. 8. The position of the potential source of pollution is marked by a solid circle. At transect A an anomaly cannot be detected around the brickworks. The maximum value at site A9 shows the influence of the city climate on the heavy metal content of soils and plants. This site lies on the weather-side of a hill chain which is situated E of GOttingen. All elements show increasing concentrations at the

different sites along the transect, corresponding to the main wind direction. Higher Pb concentrations in plants are obviously caused by the higher traffic density. At transect B an anomaly can be observed close to the brickworks. Site B I is situated on the weather side of a hill, which is 200 m N of the factory. This anomaly can only be caused by the brickworks, because no other pollutants are nearby. The fallow land the sample is taken from probably has not been fertilized. The element concentrations at the other sites are close to the background. Plants show higher concentrations at site B 10. This site lies close to a motorway. Transect C shows higher concentrations at site C 5. This was the only site, where dust sedimentation from the cementworks was seen on the leaves of trees. Site C 7 is situated in a forest N of the town. Transect D is, like transect B, situated in a rural area. In the S S W - - N N E profile increasing concentrations can be noticed behind site D 1. Sample site D 4 lies on a meadow close to the river Oder, which rises in the Harz mountains, a region with continuous lead-zinc mining. The W N W - - E S E profile shows an anomaly close to the brickworks. The element concentrations of this area are in general higher than those from transect B, even though samples of both transects are taken from rural areas. The reason may be different fertilizing. Definite evidence of heavy metal emission around brickworks is not easily shown. The brickworks are relatively small, but continuous, emitters. But when the morphological situation is unfavorable, as at transect B, where the weather side of a hill is

ppm

I~

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~o ~]" 0.8 ~o~l ~

.

o:24-~

.v'~.~.____.~ . J-"-'~\

~ " ' ~ " " ' ~

!

Pb mJ ~ " , ~ - ~ RCd

"~" " ~ . ~ . . I - ~ "

9

A

o

,.i\" J I.

0J

Cd

e--

~ e

'1

~'-~"-'--'~'-"--'~"

Cd

o J-

--

OJ,1 ?pro aZ , ~ , - . - 4 TI

Bi

o l~j

o0!ti0

.A 9 ge~2 transect C

si o., 3

~.

39

--

-"

"*--.~'

"--------~

..-.,--.,__. 678; 9 ,2 transect D

0

Table 4

H.-J. B r u m s a c k

H e a v y M e t a l C o n t e n t o f C l a y a n d B r i c k s a n d E s t i m a t i o n o f t h e L o s s (%) D u r i n g t h e B a k i n g o f t h e B r i c k s Hg ppb

Bi ppm

TI ppm

Cd ppm

Pb ppm

Zn ppm

Mn ppm

Fe %

Mg %

K %

Org. C %

clay G6ttingen (A) brick Gfttingen (A) brick corr. (Mg)

12 8 4

0.15 0.05 0.025

0.51 0.32 0.16

0.18 0.13 0.065

4.3 5.2 2.6

100 115 58

925 1210 605

4.2 4.9 2.45

1.0 2.0 1.0

2.2 2.7 1.35

23.3 001 --

loss %

66

83

69

64

40

42

clay Parensen (B) brick Parensen (B) brick corr. (Mg)

----

0.09 0.04 0.03

0.30 0.17 0.15

0.10 0.05 0.04

4.6 4.4 3.8

90 75 65

66

50

60

17

28

loss %

100 460 515 445

5.0 5.1 4.4

0.39 0.45 0.39

2.2 2.2 1.9

1.65 0.01 -100

clay Bilshausen (D) brick Bilshausen (D) brick corr. (Mg)

17 14 6

0.02 0.02 0.008

0.25 0.19 0.078

0.03 0.03 0.012

3.4 4.0 1.65

100 75 31

loss %

65

60

69

60

51

69

100

average brick (3) average loss %

11 66

0.04 70

0.23 63

0.07 61

4.5 36

88 46

0.01 100

just opposite the smoke stack, even the emissions of small brickworks can be detected very well.

Table 5

Balance between Clay and Bricks Table 4 gives the heavy metal content and some major elements in bricks and clay. During the baking of the bricks all the volatile components such as water, organics, carbon dioxide, and halogens are released. Therefore every set of samples was normalized to a constant Mg content. The heavy metal losses are between 17 and 83 percent. Especially in sample 1 the losses are very high, because of the high organic carbon content of the clay. The losses during the baking process depend on various factors. Thus the fluorine and chlorine content of the clay should have great influence on the volatilization of heavy metals.

475 475 196

2.7 3.0 1.2

0.35 0.85 0.35

2.4 2.8 1.2

0.74 0.01 --

Estimation of the Heavy Metal Release C a u s e d b y B r i c k w o r k s in W. G e r m a n y in C o m p a r i s o n t o t h e E m i s s i o n s C a u s e d b y th{ B u r n i n g o f C o a l (in t/y) pollution caused by

Hg Bi TI Cd Pb Zn

brick works

coal burning*

15 11 28 20 500 1000

24 8 7.5 60 1100 3900

"Calculated after Heinrichs 1975

Estimate of the Total Heavy Metal Emission from Brickworks in W. Germany In W. Germany the total brick production amounts to 2.4 x 107 t/y, from 4 x 107 t/y clay. Because the 3 clay samples investigated in this study do not represent the average clay, it is useful to make calculations with the well known average shale data. One calculation is based upon the average loss during the

baking process. Another calculation is based upon the theoretic: concentrations a brick would have, if the heavy metals were n~ be volatile. The difference between this theoretical data and th average concentrations found in the 3 brick sample s multiplied the annual brick production give the amounts emitted per yes The results obtained are in the same range for both calculation For comparison the amounts emitted by the burning of co (Heinrichs 1975) are listed in Table 5. The order of magnitude f~ heavy metal emission is comparable.

Metal

Table 6A

Pollution

in Samples

around

Literature Data of Contaminated and Uncontaminated Plants (Referred to Dry Matter)

Author

B o w e n (1966) L a g e r w e r f f a n d S p e c h t (1971) Goodman and Roberts (1971) S h a c k l e t t e (1972) B u r k i t t and o t h e r s (1972) Oelschlhger and Schwarz

(1972)

Bi

Cd

Pb

Zn

ppm

ppm

ppm

ppm

0.06

0.6

cont.

--

0.63-1.25

--

64.5-92.4

street, 8 m

uncont.

--

0.25-0.58

--

41.2-72.5

street, 32 m

cont.

--

9.9-40

105-814

uncont.

--

0.7--0.8

cont.

--

0.6-40

uncont. cont.

---

0.03-0.3 14

uncont.

--

2.7

Remarks

100

360-1,190

5.5-12.5 --

338

4

40

0.02

.Wagner and S i d d i q i ( 1 9 7 3 )

n.d. --

Lerche and Breckle (1974)

cont.

--

--

91-595

--

uncont.

--

--

6-27

--

rural area

little c o n t .

--

--

20-33

--

city (Sydney)

thiswork

uncont.

Table 6B

125

smelter

cont.

Noller and Smythe (1974)

--

--

-148

0.2

smelter

25

uncont, cont.

-173-256

--

3 555-19,400

-612-9,100

street, 5 m

(0.03)

0.24

8

24

--

1.0

36

100

city (G6ttingen)

rural area

heavily cont.

--

3.2

145

400

smelter

Literature Data of Contaminated and Uncontaminated Soils Bi ppm

T1 ppm

--

0.1

--

--

0.65-1.04

uncont.

--

--

0.17-0.66

cont. uncont.

---

---

26.0 0.4-0.5

--

--

cont.

--

--

uncont.

(1966)

_agerwerff and Specht (1971) Soodman and Roberts (1971)

cont.

~onnor and others (1971) B u r k i t t and o t h e r s ( 1 9 7 2 ) 3elschlhger and Schwarz

(1972)

~/an L o o n a n d o t h e r s ( 1 9 7 2 )

Cd ppm 0.06

0.81 32 0.5

Pb ppm 10

ppm

street, 8 m

50

s t r e e t , 32 m

--

17.4-

smelter

263 6-16 85

110

600

5,000

14

40

--

--

0.33

--

--

98

--

uncont.

0.21

--

--

75

---

--

--

0.4-0.6

--

--

--

0.1-0.5

--

~ / a g n e r and S i d d i q i ( 1 9 7 3 )

cont,

--

--

Lerche a n d B r e c k l e ( 1 9 7 4 )

cont. little c o n t .

---

---

---

770 145

uncont.

--

--

--

16

43

543 20-68

cont.

24-150

Remarks

55.5-192

uncont.

Shacklette and others (1971)

Zn

--

uncont.

this w o r k

smelter

little c o n t .

~uthor 3owen

Brickworks

town (Centerville) smelter

England Canada

524-4,550

228-2,030 --44

smelter street, 5 m street, 75 m USA, 863 samples rural area

uncont.

0.10

0.20

0.35

20

75

little c o n t .

0.28

0.60

1.0

80

300

city (G6ttingen)

heavily cont.

1.07

1.07

6.83

845

690

smelter

41

2

H.-J.Brumsack

Literature Comparison Table 6A and B s h o w d a t a f r o m o t h e r studies o n soil a n d plant analysis. F o r Bi a n d TI little d a t a are available. Cd d a t a s h o w a wide range for polluted samples. Difficulties in c o m p a r i n g data f r o m various a u t h o r s partly arise f r o m different s a m p l i n g procedures. F o r biological samples it is difficult to c o m p a r e values b e c a u s e the d r y m a t t e r is not well defined. It is i m p o s s i b l e to c o m p a r e dry m a t t e r d a t a with values w h i c h are b a s e d o n the a s h content.

ACKNOWLEDGMENTS I should like to t h a n k Prof. K. H. W e d e p o h l for s u p p o r t a n d discussion of this investigation. M y colleagues h a v e b e e n of great help w i t h analytical t e c h n i q u e s , especially Dr. H. H e i n r i c h s , w h o kindly carried out t h e Hg d e t e r m i n a t i o n s . I a m i n d e b t e d to Mr. R o b e r t Knight, w h o i m p r o v e d m y English. T h e D F G p r o v i d e d the ashing apparatus.

REFERENCES Alvarez, R., 1971, Orchard leaves, standard reference material 1571: Technical Note 582, p. 68-70. Bowen, H. J. M., 1966, Trace elements in biochemistry: London and New York, Academic Press, 241 p. Bowen, H. J. M., 1974, Problems in the elementary analysis of standard biological materials: Jour. Radioanal. Chem., v. 19, p. 215. Burkitt, A., P. Lester, G. Nickless, 1972, Distribution of heavy metals in the vicinity of an industrial complex: Nature, v. 238, p. 327-328. Connor, J. J., H. T. Shacklette, J. A. Erdman, 1971, Extraordinary traceelement accumulations in roadside cedars near Centerville, Missouri: U.S. Geol. Survey Prof. Paper 750 B, p. B151-B156. Goodman, G. T., and T. M. Roberts, 1971, Plants and soils as indicators of metals in the air: Nature, v. 231, p. 287. Heinrichs, H., and J. Lange, 1973, Trace element analysis and microanalysis of silicate and carbonate rocks by flameless AAS: Z. Anal. Chem., v. 265, p. 256-260. Heinrichs, H., 1975, Determination of mercury in water, rocks, coal, and petroleum with flameless AAS: Z. Anal. Chem., v. 273, p. 197-201. 1975, Die Bestimmung von Cd, Sb, Hg, TI, Pb, Bi in Gesteinen und Gewfissern mit der flammenlosen AAS: Grttingen, unpub. Ph.D. dissert., 97 p. Herrmann, A. G., and D. Knake, 1973, Coulometrisches Verfahren zur Bestimmung yon Gesamt-, Carbonat- und Nichtcarbonat-Kohlenstoff in magmatischen, metamorphen und sediment~iren Gesteinen: Z. Anal. Chem., v. 266, p. 196-201. Kaiser, H., and H. Specker, 1956, Bewertung und Vergleich yon Analysenverfahren: Z. Anal. Chem., v. p. 46. Lagerwerff, J. V., and A. W. Specht, 1971, Occurrence of environmental cadmium and zinc, and their uptake by plants: Columbia, Mo., Proc. 4th Annual Conference on Trace Substances in Environmental Health, p. 85-93. Lerche, H., and S.-W. Breckle, 1974, Blei im Okosystem Autobahnrand A Naturwissenschaften, v. 61, p. 218. -

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Noller, B. N., and L. E. Smythe, 1974, Distribution of lead in vegetat~ bordering roads in the Sydney Metropolitan Area: Search, v. 5, 108-110. Oelschlfiger, W., and E. Schwarz, 1972, Fehlermrglichkeiten und der Eliminierung bei der Bestimmung yon Blei mittels Dithizon in bi0: gischen Substanzen: Z. Anal. Chem., v. 258, p. 203-207. Peirson, D. H., P. A. Cawse, L. Salmon, and R. S. Cambray, 1973, Tra elements in the atmospheric environment: Nature. v. 241, p. 252-~ Ruppert, H., 1975, Geochemical investigations on atmospheric precipi: tion in a medium-sized city (G/3ttingen, F.R.G.): Water, Air, and Pollution, v. 4, p. 447-460. Schramel, P., 1973, Determination of eight metals in the internati0t biological standard by flameless AAS: Analytica Chimica Acta, v.l p. 6%77. Segar, D. A., and J. L. Gilio, 1973, The determination of trace transit elements in biological tissues using flameless atom reservoir at0~ absorption: Internat. Jour. Environ. Anal. Chem., v. 2, p. 291-301. Shacklette, H. T., J. C. Hamilton, J. G. Boerngen, and J. M. Bowl: 1971, Elemental composition of surficial materials in the conterminc United States: U.S. Geol. Survey Prof. Paper 574 D, 71 p. Shacklette, H. T., 1972, Cadmium in plants, U.S. Geol. Survey Pr, Paper 1314 G, 28 p. Van Loon, J. C., J. Lichwa, and D. Ruttan, 1973, A study oft determination and distribution of cadmium in samples collected heavily industrialized and urbanized region (Metropolitan Toront Internat. Jour. Environ. Anal. Chem., v. 3, p. 147-160. Wagner, K.-H., and J. Siddiqi, 1973, Schwermetallkontamination dur industrielle Immission: Naturwissenschaften, v. 60, p. 161. Wahler, W., 1964, Mechanische und chemische Aufbereitung yon Min~ alen and Gesteinen fiir geochemische Spurenanalysen: N. Jb. Min al. Abh.. v. 101, p. 109-126. Wedepohl, K. H. (ed.), 1969, Handbook of geochemistry: Bert Heidelberg-New York, Springer-Verlag, 442 p. 1969, Die Zusammensetzung der Erdkruste: Fortschr. Miner.. 46, p. 145-174. Williams, C. H., and D. J. David, 1973, The effect of superphosphate the cadmium content of soils and plants: Australian Jour. Soil Res. 11, p. 43. -

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