Chemical compositions and sources of organic matter in fine particles of soils and sands from the...

Environmental Monitoring and Assessment (2006) 120: 537–557

DOI: 10.1007/s10661-005-9102-8 c© Springer 2006

CHEMICAL COMPOSITIONS AND SOURCES OF ORGANIC MATTERIN FINE PARTICLES OF SOILS AND SANDS FROM THE VICINITY

OF KUWAIT CITY

AHMED I. RUSHDI1,∗, SHEIKHA AL-ZARBAN2 and BERND R. T. SIMONEIT1

1Environmental and Petroleum Geochemistry Group, College of Oceanic and Atmospheric Sciences,Oregon State University, Corvallis, Oregon, U.S.A.; 2Department of Biological Sciences, College of

Sciences, Kuwait University, Kuwait(∗author of correspondence, e-mail: [email protected])

(Received 24 December 2004; accepted 4 November 2005)

Abstract. Fine particles in the atmosphere from soil and sand resuspension contain a variety of

organic compounds from natural biogenic and anthropogenic matter. Soil and sand samples from

various sites near Kuwait city were collected, sieved to retain the fine particles, and extracted with

a mixture of dichloromethane and methanol. The extracts were derivatized and analyzed by gas

chromatography-mass spectrometry in order to characterize the chemical compositions and sources

of the organic components. The major inputs of organic compounds were from both natural biogenic

and anthropogenic sources in these samples. Vegetation was the major natural source of organic com-

pounds and included n-alkanols, n-alkanoic acids, n-alkanes, sterols and triterpenoids. Saccharides

had high concentrations (31–43%) in the sand dune and seafront samples, indicating sources from

decomposed vegation materials and/or the presence of viable microbiota such as bacteria and fungi.

Vehicular emission products, leakage of lubricating oils, discarded plastics and emissions from cook-

ing operations were the major anthropogenic inputs in the samples from the urban areas. This input

was mainly UCM, n-alkanes, hopanes, plasticizers and cholesterol, respectively.

Keywords: hopanes, lipids, plasticizers, saccharides, sterols, UCM

1. Introduction

The major sources of organic compounds in urban environments are emissions fromfossil fuel use, smoke from food preparation, industry and biomass burning, andinputs from natural terrestrial vegetation (wax) in coastal areas from marine lipids,with secondary products derived from the oxidation of atmospheric organic matter(Matsumoto and Hanya, 1980; Simoneit, 1980, 1984, 1986, 1989, 1999; Simoneitand Mazurek, 1982, Mazurek et al., 1989; Rogge et al., 1991, 1993a, 1997a,b, 1998;Fraser et al., 1997, 1998a,b). Lipids, soot and humic and fulvic acids from biogenicand anthropogenic sources are also recognized to be a major carbonaceous fractionin the various ecospheres (Simoneit, 1977, 1980, 1984, 1986, 1989, 1999; Ketseridiset al., 1976; Broddin et al., 1980; Marty and Saliot, 1982; Simoneit and Mazurek,1982, 1989; Gagosian and Peltzer, 1986; Cass et al., 1993; Rogge et al., 1993a;Schauer et al., 1996). The organic tracer compounds are drived from: (1) lipids

538 A. I. RUSHDI ET AL.

of terrestrial higher plants, marine biota and urban activities (e.g., cooking); (2)sugar-derivatives, methoxyphenols and resin acids from biomass burning; (3) n-alkanes and n-alkanols from higher plant waxes; (4) dicarboxylic acids and otherpolar oxidation products; and (5) polynuclear aromatic hydrocarbons (PAH) fromcombustion processes (Simoneit, 1980, 1984, 1986, 1989; Simoneit and Mazurek,1982; Gagosian et al., 1987; Standley and Simoneit, 1987; Simoneit et al., 1988,1990, 1991a,b,c, 1993, 1999; Rogge et al., 1991, 1993a–e, 1994, 1996, 1998; Abaset al., 1995; Abas and Simoneit, 1996; Fraser et al., 1997; 1998a,b).

Soil resuspension by natural and man-made processes is another source of inputof organic matter to the atmosphere (e.g., Simoneit 1980; Rogge et al., 1993c;Al-Mutlaq et al., 2002; 2005; Rushdi et al., 2005). This can occur by local particleresuspension, agriculture and construction related operations, road dust in urban andrural areas, as well as transport from desert and semi-arid regions such as the ArabianPeninsula. Surface soils, sands and road dusts contain organic matter derived frommany sources, which have not been characterized for the Kuwait region. Thus,the major purpose of this paper is to identify the higher molecular weight organictracers in the fine particles of surface soils and sands from Kuwait city. It is anattempt to evaluate one potential source of organic matter in the atmosphere of thisregion.

2. Experimental Methods

2.1. SAMPLING AND EXTRACTION PROCEDURE

Seven soil and sand samples were collected from the surrounding area of Kuwaitcity in Feberuary 2004 to characterize their organic matter contents by gaschromatography-mass spectrometry (GC-MS) analysis. The locations and the de-scriptions of the samples are shown in Figure 1 and Table I. The samples werecollected from sites outside the main city, which represent rural areas ranging frompopulated with different human activities such as public markets (MP) and heavyvehicular traffic (HW and BS) sites to public parks (PK) and seafront places (SF)where human activities are limited to leisure time. One sample was collected froma sand dune in a less populated area of the city (SD).

The samples were treated the same way as described by Rushdi et al. (2005).Each sample was sieved to obtain fine particles (<125 μm) before total organicmatter extraction. The extraction was conducted twice by adding a mixture ofmethylene chloride/methanol (3:1 v/v) to about 2–5 g of the sieved fine particles ofeach sample and ultrasonicating for 20 min. The extracts were filtered through

pre-extracted glass microfiber filters (WhatmanR©

, GF/A filters) before solventcollection. Each total extract was then concentrated under nitrogen blow-downat room temperature to approximately 1.0–1.5 mL before GC-MS analysis. Analiquot (50–100 μL) of each total extract was derivatized with silylating reagent

CHEMICAL COMPOSITIONS AND SOURCES OF ORGANIC MATTER 539

Figure 1. Map showing the sampling locations of the sand and soil samples.

[N,O-bis(trimethylsilyl)trifluoroacetamide, BSTFA, Pierce Chemical Co] beforeanalysis by GC-MS. This derivatizing agent replaces the H in hydroxyl groupswith a trimethylsilyl [(CH3)3Si, i.e. TMS] group for better GC resolution of polarcompounds.


TABLE I

Descriptions and locations of the soil and sand samples collected from rural Kuwait city

Sample code Location Description

HW Highway outside the city Mixture of soil and sand

MP Market place in rural area of the city Mostly soil

PK Public park outside the city Mostly soil

BS Bus station in the vicinity of the city Mixture of soil and sand

SW Side walk in the rural area of the city Mixture of soil and sand

SF Sea front outside the city Sand

SD Sand dune outside the city Sand

2.2. INSTRUMENTAL ANALYSIS

The analysis of the extracts was carried out by GC-MS, using a Hewlett-Packard6890 GC coupled to a 5973 Mass Selective Detector with a DB-5MS (Agilent)fused silica capillary column (30 m × 0.25 mm i.d., 0.25 μm film thickness) andhelium as carrier gas. The GC was temperature programmed from 65◦ C (2 mininitial time) to 300◦ C at 6◦ C min−1 (isothermal for 20 min final time). The MSwas operated in the electron impact mode at 70 eV ion source energy. Data wereacquired and processed with a Hewlett-Packard ChemStation.

Compounds were identified by GC retention index and MS comparison with au-thentic standards, literature and library data, and characterized mixtures. Unknowncompounds were characterized by interpretation of the fragmentation pattern oftheir mass spectra. The concentrations of the compounds in ng g−1 sample wereestimated from ratios peak areas in the total ion current traces.

3. Results

The compositions of the total extracts of the fine particles of soil and sand fromKuwait city rural area are given in Table II. The extracts are mixtures of n-alkanes,n-alkanols, n-alkanoic acids, hopanes, terpenoids, sterols, carbohydrates and plas-ticizers (Figure 2).

The concentrations of the total n-alkanes, ranging from C17 to C34, were0 to 4.7 μg g−1 sample with maximum concentrations (Cmax) of heptacosane (C27),nonacosane (C29), or hentriacontane (C31) (Table II, Figure 3a ). The odd num-bered n-alkanes were dominant in the PK and SW samples with carbon prefer-ence indices (CPI, Bray and Evans, 1961) ranging from 0.90 and 7.92. Sample BS(Figure 3b) showed essentially no carbon number predominance with a CPI value of0.90.


TABLE II

Composition, concentration (ng g−1 sample) and various parameters of solvent-extractable organic

matter of sands and soil fine particles from the vicinity of Kuwait city

Sample code

Compound Composition M.W. HW MP PK BS SW SF SD

n-Alkanes

Heptadecane C17H36 240 T T nd 6 nd nd nd

Octadecane C18H38 256 T T nd 17 nd nd nd

Nonadecane C19H40 268 T T nd 43 nd nd nd

Eicosane C20H42 282 T T nd 64 nd nd nd

Heneicosane C21H44 296 T T nd 72 nd nd nd

Docosane C22H46 310 T T nd 104 nd nd nd

Tricosane C23H48 324 T T nd 188 nd nd nd

Tetracosane C24H50 338 T T nd 260 nd nd nd

Pentacosane C25H52 352 T T 19 289 nd nd nd

Hexacosane C26H54 366 T T 9 22.5 nd nd nd

Heptacosane C27H56 380 T T 159 231 20 nd nd

Octacosane C28H58 394 T T 2 739 T nd nd

Nonacosane C29H60 408 T T 267 451 49 nd nd

Triacontane C30H62 422 T T 74 682 T nd nd

Hentriacontane C31H64 436 T T 225 592 62 nd nd

Dotriacontane C32H66 450 T T nd 349 T nd nd

Tritriacontane C33H68 464 T T nd 384 nd nd nd

Tetratriacontane C34H70 478 T T nd 43 nd nd nd

Totala T T 750 4740 132 nd nd

(9.6) (17.7) (4.8)

CPI (o/e)b 7.92 0.91

Pristane C19H40 268 nd nd nd 6 Nd nd nd

Phytane C20H42 282 nd nd nd 23 Nd nd nd

Pr/Ph 0.25

n-Alkanols

Hexadecanol C16H34O 242 Nd nd T nd nd nd nd

Octadecanol C18H38O 270 Nd nd T nd nd nd nd

Eicosanol C20H42O 298 Nd nd T nd T nd nd

Docosanol C22H46O 326 Nd nd T nd T nd nd

Tetracosanol C24H50O 354 Nd nd 54 nd 17 nd nd

Pentaconsanol C25H52O 368 Nd nd 38 nd 8 nd nd

Hexacosanol C26H54O 382 Nd nd 172 347 62 nd nd

Heptacosanol C27H56O 396 Nd nd 196 T 57 0 nd

Octacosanol C28H58O 410 Nd 1340 597 407 220 201 71

(Continued on next page)


TABLE II

(Continued)

Sample code


Nonaconsanol C29H60O 424 Nd nd 266 T 71 nd nd

Triacontanol C30H62O 438 Nd 1189 992 670 294 260 100

Hentriacontanol C31H64O 452 Nd nd 201 T 67 nd nd

Dotriacontanol C32H66O 466 Nd nd 446 4.3 116 nd nd

Tritriacontanol C33H68O 480 Nd nd 9 nd nd nd

Tetratriacontanol C34H70O 494 Nd nd 64 nd nd nd nd

Totala 2530 3034 1467 914 550 171

(2.2) (37.7) (5.1) (38.5) (30.8) (32.5)

n-Alkanoic acids

Tetradecanoic acid C14H28O2 228 89 93 25 58 11 nd nd

Pentadecanoic acid C15H30O2 242 47 47 32 nd nd nd

Hexadecanoic acid C16H32O2 256 588 1002 144 633 77 150 72

Heptadecanoic acid C17H34O2 270 83 175 95 nd nd nd

Octadecanoic acid C18H36O2 284 688 1248 102 690 45 111 15

Nonadecanoic acid C19H38O2 298 190 350 98 nd nd nd

Eicosanoic acid C20H40O2 312 119 909 471 nd nd nd

Heneicosanoic acid C21H42O2 326 647 548 nd nd nd nd nd

Docosanoic acid C22H44O2 340 847 1061 nd nd nd nd nd

Tricosanoic acid C23H46O2 354 516 2938 nd nd nd nd nd

Tetracosanoic acid C24H48O2 368 641 1259 nd nd nd nd nd

Pentacosanoic acid C25H50O2 382 368 688 nd nd nd nd nd

Hexacosanoic acid C26H52O2 396 920 1866 nd nd nd nd nd

Totala 5745 12185 271 2077 133 261 93

(9.7) (10.5) (3.5) (7.2) (4.9) (14.6) (17.6)

CPIc 2.05 1.55 – 7.96 – – –

12-Hydroxystearic acid C18H36O3 300 1080 nd nd nd nd nd nd

Triterpenoids

α-Amyrin C30H50O 426 10 36 151 T 77 nd nd

β-Amyrin C30H50O 426 4 13 63 T 59 nd nd

Totala 14 49 214 T 136 nd nd

(1.2) (0.4) (2.7) (5.0)

Steroids

Cholesterol C27H46O 386 0 nd 146 289 nd nd nd

Campesterol C28H48O 400 0 nd 152 nd nd nd nd

Stigmasterol C29H48O 412 0 nd 165 286 nd nd nd

Sitosterol C29H50O 414 504 nd 340 347 121 nd nd



TABLE II

(Continued)

Sample code


Totala 504 804 921 121 nd nd

(0.9) (10.3) (3.2) (4.4)

Saccharides

α-Fructose C6H12O6 180 T T nd T nd 2 nd

β-Fructose C6H12O6 180 T T nd T nd 12 nd

α-Glucose C6H12O6 180 30 23 nd 14 nd 22 nd

β-Glucose C6H12O6 180 24 35 nd 32 nd 20 nd

Sucrose C12H22O11 342 398 1388 nd 598 nd 170 120

Mycose C12H22O11 342 760 1807 129 589 274 321 102

Totala 1223 3253 129 1233 274 546 222

(2.1) (2.8) (1.7) (4.3) (10.6) (30.6) (41.9)

Hopane biomarkers

Trisnorneohopane C27H46 370 659 1492 T 231 0.3 nd nd

17α(H)-Trisnorhopane C27H46 370 617 1294 T 321 0.3 nd nd

17α(H),21β(H)-

Norhopane

C29H50 398 1941 3906 T 869 57 90 nd

17α(H),21β(H)-

Hopane

C30H52 412 1893 3218 T 489 38 48 nd

17α(H),21β(H)-22S-

Homohopane

C31H54 426 1045 1586 nd 352 36 39 nd

17α(H),21β(H)-22R-

Homohopane

C31H54 426 1163 1737 nd 479 54 27 nd

17α(H),21β(H)-22S-

Bishomohopane

C32H56 440 1234 1924 nd 338 28 42 nd

17α(H),21β(H)-22R-

Bishomohopane

C32H56 440 611 886 nd 208 26 44 nd

17α(H),21β(H)-22S-

Trishomohopane

C33H58 454 629 1283 nd 142 nd nd nd

17α(H),21β(H)-22R-

Trishomohopane

C33H58 454 861 711 nd 130 nd nd nd

17α(H),21β(H)-22S-

Tetrakishomohopane

C34H60 468 374 490 nd 92 nd nd nd

17α(H),21β(H)-22R-

Tetrakishomohopane

C34H60 468 475 361 nd 90 nd nd nd

17α(H),21β(H)-22S-

Pentakishomohopane

C35H62 482 225 303 nd 87 nd nd nd

17α(H),21β(H)-22R-

Pentakishomohopane

C35H62 482 101 47 nd 75 nd nd nd

Total 11828 19239 nd 3902 239 315 nd

(19.9) (16.5) (13.2) (8.8) (17.7)



TABLE II

(Continued)

Sample code


C31 S/(R+S) 0.47 0.48 0.42 0.39 2.35

C32 S/(R+S) 0.67 0.68 0.62 0.52 1.67

Steranes

14β,17β-20R-

Cholestane

C27H48 372 T 2227 T T T nd nd

14β,17β-20R-

Methylcholestane

C28H50 386 nd 1901 nd nd nd nd nd

14α,17α-20S-24-

Ethylcholestane


14β,17β-20R-24-

Ethylcholestane


14β,17β-20S-24-

Ethylcholestane


14α,17α-20R-24-

Ethylcholestane

C29H52 400 nd nd nd nd nd nd

Totala T 10272 T T T nd nd

(8.8)

Plasticizers

Diethyl phthalate C12H14O4 222 T T T 14 T T T

Dibutyl phthalates C16H22O4 278 T T T 38 T T T

Benzyl-butyl

Phthalate

C19H20O4 312 nd nd nd 321

Dioctyl phthalates C24H38O4 390 4196 2542 350 1753 105 70 32

Dinonyl phthalates C26H42O4 418 5045 6075 T 1872 105 70 32

Totala 9241 8617 350 3998 105 70 32

(15.6) (7.4) (4.5) (13.8) (3.9) (3.9) (6.0)

UCM 29566 60749 247851 10903 694 36 10

(49.82) (52.1) (30.6) (37.8) (25.5) (2.0) (1.8)

Total all compounds 59401 117335 7821 29068 2725 1820 533

aThe relative concentrations of the compound groups are given in parentheses.bCPI = ∑

(nC17 + · · · + nC33)/∑

(nC18 + · · · + nC34).cCPI = ∑

(nC16 + · · · + nC26)/∑

(nC15 + · · · + nC25).

nd: not detected.

The n-alkanols were major compounds with total concentrations ranging from0 to 2.5 μg g−1 sample, extending from C24 to C34 (Figure 3c), with Cmax ofhexacosanol (C26), octacosanol (28) or nonacosan-10-ol (29). The n-alkanoic acidconcentrations varied from 0.1 to 12.0 μg g−1 sample (Table II), ranging from C11 toC26, and with a Cmax of hexadecanoic (16) and octadecanoic (18) acids (Figure 3d).The even carbon numbered homologs of the n-alkanoic acids and n-alkanols were


dominant (Table II). Methyl n-alkanoates and n-alkan-2-ones were not found inthese samples.

α- and β-Amyrins were present in these samples (Figure 3e), with concen-trations of 0–214 ng g−1 sample. Steroids, comprised of cholesterol, campesterol,stigmasterol and sitosterol, were significant only in sample PK (Figure 3f) and attraces in the other samples from the city. Saccharides (carbohydrates) were principal

Figure 2. GC-MS total ion current traces of total extracts (silylated) of the sand and soil samples from

Kuwait city rural showing the major organic components: (a) HW (high-way); (b) PK (public park);

(c) BS (bus station); and (d) SW (sidewalk) (Numbers refer to the carbon number and symbols are: I

= di-iso-butyl-, II = di-n-butyl-, III = benzyl-n-butyl- and IV = diethylhexyl-phthalate (octoil), and

UCM = unresolved complex mixture).



Figure 2. (Continued)

compounds in these samples and included α- and β-fructose, α- and β-glucose, su-crose and mycose (Figure 3g). The concentrations of the carbohydrates ranged from0.1 to 3.3 μg g−1 sample.

The UCM (unresolved complex mixture of branched and cyclic compounds)was obvious in these samples and varied in concentration from 1.0 to 67 μg g−1

sample.Hopane biomarkers, ranging from C27 to C35 with a Cmax at 29, were found in all

samples (e.g., Figure 4a) except samples PK and SD. Their concentrations rangedfrom 0 to 19.2 μg g−1 sample. Only traces of sterane biomarkers were detectable inall samples except samples SF and SD and included the typical C27 to C29 steranes(e.g., Figure 4b). Plasticizers, including diethyl-, dibutyl-, and dioctyl-phthalates


were detected at concentrations of 0.03–4.20 μg g−1 sample, with the latter as amajor component (Figure 4c). 12-Hydroxystearic acid, which is industrial chem-ical, was detected only in the highway sample (HW) and the concentration was1.1 μg g−1 sample.

Figure 3. Examples of typical GC-MS key ion plots for various compound series found in the sand

and soil samples: (a) PK, m/z 85 n-alkanes (CPI = 7.92); (b) BS, m/z 85 n-alkanes (CPI = 0.90);

(c) PK, m/z 103 n-alkanols as TMS ethers; and (d) MP, m/z 117 n-alkanoic acids as TMS esters; (e)

SW, m/z 218, triterpenoids (TMS); (f) PK, m/z 129 (TMS), sterols (TMS); (g) SF, m/z 204, 217, 361,

saccharides (TMS) (numbers and symbols as in Figure 2). (Continued on next page)



4. Discussion

The organic geochemical analysis results of the fine particle samples of soil and sandfrom rural Kuwait show that biogenic and anthropogenic input are the major sources.These sources are from regional vegetation, vehicle emissions and surroundingrural activities. The presence of a mixture of various lipid compound classes andcarbohydrates in the total extracts is an indication of the natural biogenic sources,mainly from the surrounding vegetation, microbial biomass and detrital organic



matter. The occurrences of an UCM, hopane and sterane biomarkers, n-alkanes, andplasticizers indicate the anthropogenic sources from petroleum product utilizationand human activities.

4.1. NATURAL BIOGENIC SOURCES

The occurrence of wax lipids, such as n-alkanes, n-alkanoic acids, n-alkanols,triterpenoids, and phytosterols, supports the natural source input from higher plantbiomass (Simoneit, 1980, 1986; Gagosian and Peltzer, 1986; Abas and Simoneit,1996). This is based on the Cmax mainly at nonacosane (C29) and/or hentriacontane



(C31) and the odd carbon number preference (CPI > 1) of the n-alkanes >C23, bothdistinctive of higher plant waxes (e.g., Table II, Figure 3a, Simoneit, 1989). Thepresence of the long chain n-alkanols and n-alkanoic acids (>C20) in the lipids,with primarily only the even carbon number homologs is another indicator forplant wax (e.g., Figure 3c,d, Simoneit, 1977, 1989). The n-alkanoic acids with astrong even carbon number predominance and Cmax at 16 and 18, are from multiplesources including urban activity, microbiota, and vascular plant waxes, cutin andsuberin (Simoneit, 1977, 1989, 1999; Holloway, 1982). The absence of unsaturatedalkanoic acids indicates extensive oxidation and biodegradation of the lipid matterof the sand or soil particles. This is also indicated by the absence of n-alkanes fromvehicular emissions (cf. sample HW), which appear to have been biodegraded inthe surface environment (Simoneit, 1984).

The presence of even carbon numbered n-alkanols ranging from C24 to C34

with a Cmax at 30 (Figure 3c) indicates an input of vascular plant wax from atypical tropical desert environment (Simoneit, 1977, 1989). The α- and β-amyrinsare triterpenoids derived from higher vascular plant waxes and detritus (Simoneit,1989) (Figure 3e, Table II). The phytosterols in the samples (e.g., Figure 3f) fromthe public park (PK) and bus station (BS) in the city, consisting mainly of theC29 compounds, are derived from vegetation (Simoneit et al., 1983). However, thesignificant concentration of cholesterol in the urban area indicates an input fromcooking emissions (Rogge et al., 1991).

Saccharides are major components in all samples from the vicinity of the city(Table II, Figure 3g). Extracellular carbohydrates, microbial and fungal biomass(Lehninger, 1970), and degradation of detrital cellulose from various natural and


anthropogenic components are major sources of the carbohydrates in the environ-ment. These carbohydrates are mainly α- and β-fructose, α- and β-glucose, sucrose,and mycose. Various agricultural soils have been analyzed for saccharide contents,and glucose and sucrose are typical for all biomass and mycose for microbial andfungal biomass (Al-Mutlaq et al., 2005; Rogge et al., 2004; Rushdi et al., 2005;Simoneit et al., 2004). Levoglucosan, the major tracer from biomass burning emis-sions (Simoneit et al., 1999) is not detectable in any sample, indicating ash fall-outfrom fires is not significant in the rural area.

The dominant organic compound groups from natural biogenic sources in thesesoil and dust samples include carbohydrates (1.7–43.1%) from microbiota and plantdetritus, and the lipids as n-alkanols (2.2–38.5%), n-alkanoic acids (3.5–17.6%),

Figure 4. Examples of typical GC-MS key ion plots for biomarkers and plasticizers in the surface

sand and soil samples: (a) MP, m/z 191 hopanes; (b) MP, m/z 217+218 steranes; and (c) SW, m/z 149

plasiticizers (carbon numbers and symbols as in Figure 2). (Continued on next page)



sterols (0.0–10.3%) and n-alkanes (in part), (0–16.4%) all from higher plant waxand detritus. This is summarized in Figure 5a.

4.2. ANTHROPOGENIC SOURCES

n-Alkanes, biomarkers (e.g., hopanes and steranes, Figure 4a, b, respectively,Table II), and UCM from fossil fuel components indicate anthropogenic inputsfrom traffic emissions (Broddin et al., 1980; Marty and Saliot, 1982; Simoneit,1984). Anthropogenic inputs from litter (plastics) are also evident from the highphthalate contents (Figure 4c, Table II). The n-alkanes with no carbon number pre-dominance (i.e., CPI ∼ 1.0, after subtraction of the n-alkane contribution from plantwax, Simoneit et al., 1991a), support the source from vehicle emissions and arefound mainly in the sample from the bus station. However, the low ratio of petroleumderived n-alkanes to UCM for most samples indicates extensive biodegradation inthe environment (Simoneit, 1984). The hopanes, with typical values of (S/(S+R))C31 and C32 hopane indices (Table II), and trace sterane biomarkers detected inall the samples further confirm the emissions from petroleum product utilization(Simoneit, 1984). The UCM is the major petroleum component derived from lu-bricating oils in vehicle emissions and direct oils leakage from vehicles (Table II).Petroleum residues were found mainly in the samples from the highway, bus sta-tion and market place (HW, BS, MP), where heavy traffic is typical. Petroleumcomponents were not detected in remote locales with less human activities such asin the sample from the sand dune (SD). The absence of significant concentrationsof PAHs indicates that organic compounds from combustion processes (Simoneit,1998) are not a major input.


Figure 5. Relative concentrations (as %) of the main groups of organic compounds in the soil and

sand samples: natural versus anthropogenic sources.

The major organic compound classes from anthropogenic sources are UCM(1.8–60.1%), hopanes (0–20.0%), n-alkanes (0–15.7%), steranes (0–8.8%) all fromvehicle emissions and spills of petroleum related compounds such as lubricating oil,and plasticizers (2.2–7.1%) from plastic refuse as shown in Figure 5b. Obviously,the contribution of anthropogenic versus natural biogenic sources varies and de-pends on the impact of rural activities on a location as illustrated in Figure 6. Theanthropogenic sources ranged from 8 to 88%, with the highest levels in sites closerto the city and highways (37–88%) and lowest in areas away from the city (7–24%).


Figure 6. The percent fractions of natural versus anthropogenic organic matter sources in the soil and

sand samples.

5. Conclusion

The fine particles of sand and soil analyzed from the vicinity of Kuwait containorganic compounds from both natural biogenic and anthropogenic sources. Thenatural organic compounds are derived mainly from higher plant waxes (i.e., localvegetation) and include n-alkanols, n-alkanoic acids, n-alkanes, triterpenoids, andphytosterols. Their concentrations are lower in the samples from locales with heavyurban traffic.

The anthropogenic sources are characterized by the presence of n-alkanes withCPI ∼ 1, hopane and sterane biomarkers, and UCM from urban traffic emissions,plasticizers from litter and detritus (e.g., shopping bags), and cholesterol fromcooking emissions. The abundance of anthropogenic organic matter in the samplesdepends on the location and the types of human activities. They are at trace levelsin public parks and away from the city.

Acknowledgments

S.A. would like to thank Mr. Mohammad Al-Mishwat for collecting the samples.


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