Organic marker compounds for surface soil and fugitive dust from open lot dairies and cattle...

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Atmospheric Environment 40 (2006) 27–49

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Organic marker compounds for surface soil and fugitive dustfrom open lot dairies and cattle feedlots

Wolfgang F. Roggea,�, Patricia M. Medeirosb, Bernd R.T. Simoneitb

aDepartment of Civil and Environmental Engineering, Florida International University, Miami, FL 33199, USAbEnvironmental and Petroleum Geochemistry Group, College of Oceanic and Atmospheric Sciences, Oregon State University,

Corvallis, OR 97331, USA

Received 20 April 2005; received in revised form 10 July 2005; accepted 10 July 2005

Abstract

Fugitive dust emissions from cattle feedlots and open lot dairies are substantial. In order to determine the contribution

of intensive cattle operations on ambient PM levels, more knowledge besides the elemental composition is necessary in

order to distinguish between airborne PM from nearby agricultural fields, barren lands, or dirt roads. Here, as part of the

San Joaquin Valley Fugitive Dust Characterization Study, surface soil samples collected from feedlots and open lot dairy

farms are investigated for potential source specific molecular marker compounds. More than 100 organic compounds were

quantified including: n-alkanes, n-alkanoic acids, n-alkenoic acids, n-alkanols, n-alkanals, n-alkan-2-ones, steroids,

triterpenoids, isoprenoids, and tocopherols (vitamin E) and metabolites. Biohydrogenation of plant lipids and sterols in the

rumen results in distinctive alteration products. Animal and plant derived steroids are most abundant. Here, it is shown

that 5b-stigmastanol and epi-5b-stigmastanol, two biohydrogenation products of sitosterol and stigmasterol, are the most

distinctive molecular marker compounds. While stearic (C18) and palmitic (C16) acids are as individual compounds not

source specific, biohydrogenation of the more abundant C18 unsaturated fatty acids, causes the ratio of C18/C16 fatty acids

to shift from below 0.5 for vegetation to an average of 3.070.7. Consequently, the C18/C16 fatty acid ratio is unique and

can be used as well in source apportionment studies.

r 2005 Elsevier Ltd. All rights reserved.

Keywords: Concentrated animal feeding operations; Tocopheryl acetate metabolites; 5b-stigmastanol; epi-5b-Stigmastanol; Fatty acids;

epi-Coprosteroids; Coprostanol; epi-Coprostanol; Phytosterols; Phytostanols

1. Introduction

In the San Joaquin Valley of California, 40–60%of the ambient PM10 concentrations have beensuggested to be the result of agricultural activities(Chow et al., 1992, 1993; Clausnitzer and Singer,

e front matter r 2005 Elsevier Ltd. All rights reserved

mosenv.2005.07.076

ing author. Tel.: +1305 348 6755;

2802.

ess: [email protected] (W.F. Rogge).

2000). Major contributions of these mainly fugitivesources are related to wind blown dust fromagricultural fields post harvesting and agriculturalactivities such as tilling, harvesting, and traffic overunpaved roads. Likewise, cattle husbandry in openlot dairies and beef cattle feedlots are major sourcesof fugitive dust, including the inhalable fractions(PM10 and PM2.5).

In the United States, animal farming has changeddramatically over the last century. Since World War

.

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ARTICLE IN PRESSW.F. Rogge et al. / Atmospheric Environment 40 (2006) 27–4928

II, cattle raising is shifting away from farms thatwere limited by their own fodder production tolarge industrialized feeding operations that mainlybuy their cattle fodder (Gregory, 2000; Hinrichs andWelsh, 2003; Subak, 1999). In 2003, about 96million cattle and calves were raised in the UnitedStates in pastures, dairy farms, and feedlots(USDA, 2004). Today, more than 20 million cattleare raised annually for fattening in feedlots thatoften hold several tens of thousands of cattle at atime. Typically, cattle stay about 80–150 days forfattening in feedlots. Within the San Joaquin Valley,the cattle population consists of nearly 2 milliondairy cattle, about 400,000 range cattle, and close to300,000 beef cattle raised in feedlots.

Open lot concentrated cattle operations in theUSA generate about 18 million metric tons ofcollectable manure/year (USDA, 2000). The solidand liquid waste generated from cattle farm opera-tions have a pronounced impact on nearby surfaceand ground water quality, as well as soil contam-ination and air pollution. Major contaminants arenitrate, phosphate, veterinary agents, natural ster-oidal estrogen hormones, pesticides, pathogenicmicroorganisms and resulting endotoxins, petro-leum related exhaust from farm vehicles, organicdust from feedlot surface soil and dried manure,dust from fodder receiving, loading and processingoperations, ammonia (NH3) that leads to secondaryaerosol formation with subsequent acidic aerosoldeposition, reactive organic gases (ROG) thateventually lead to ozone and secondary organicaerosol formation, green house gases such as carbondioxide (CO2), methane (CH4), nitrous oxide (N2O),odorous compounds such as H2S, amides, volatileorganic acids, mercaptans and others (e.g., Gintinget al., 2003; Goss et al., 1998; Hanselman et al.,2003; Hartung, 1998; Hintz and Linke, 1998;Jjemba, 2002; Lammel et al., 2004; Larney et al.,2003; McGinn et al., 2002, 2003; NRC, 2003;Phetteplace et al., 2001; Saintfort et al., 1995; Scottet al., 2003; Shaw et al., 1998; Subak, 1999; Takaiet al., 1998; Todd et al., 2004; USDA, 2000).

While the impact of cattle feedlots and dairyfarms on surface and ground water quality hasreceived appreciable attention in the past, little isknown about the impact of fugitive dust on localand regional air quality. In epidemiological andclinical studies, organic dusts from animal husban-dries have been related to allergic rhinitis, occupa-tional farmer asthma, chronic obstructivepulmonary disease, other respiratory diseases, and

cancer (e.g., Bessot et al., 1996; Cathomas et al.,2002; Kauppinen et al., 1992; Molocznik, 2002;Molocznik and Zagorski, 2001; Radon et al., 2001;Rautiainen et al., 1997). Similarly, cattle haveexhibited respiratory distress that is believed to berelated to the organic dust, fungi and bacteriaassociated with manure dust particles, and otheragents (McVean et al., 1986; Purdy et al., 2004;Sorenson et al., 1992; Woolums et al., 2001).Likewise, it has been suggested that intensivelivestock operations impair the quality of life ofnearby residents mainly from airborne dust andodor nuisances (McGinn et al., 2002, 2003; Purdyet al., 2004; Sweeten and Miner, 1993; Wing andWolf, 2000).

As part of the San Joaquin Valley Fugitive DustCharacterization Study, 47 surface soil sampleswere collected by Ashbaugh and coworkers (2003)from agricultural fields growing major crops,feedlots, dairy farms, construction sites, as well asdust from paved and unpaved roads. These soil dustsamples were characterized for moisture content,particle-size distribution, dry silt content, nitrogenand carbon content, and PM10 as well as PM2.5index (Ashbaugh et al., 2003; Carvacho et al., 2001).Chow and coworkers (2003) used a resuspensionapparatus to generate PM10 samples that wereanalyzed for 40 elements, EC, OC, and seven watersoluble ions. According to the above investigations,the surface soils from the feedlots and open lotdairies were classified as mainly organic. Com-monly, soil dusts from agricultural fields are oftennot distinguishable from each other or from desertderived airborne dust particles based solely on theirmajor elemental composition. Thus, adding specificorganic marker compounds to the bulk chemical,ionic, and elemental data of the fugitive dust sourceprofiles allows discrimination of fugitive dust sourcecontributions to a given site of interest (Rogge,2000).

The detailed organic chemical composition ofsurface soils from cattle husbandries has previouslynot been determined, and therefore, it is the scope ofthis study. If unique organic compounds can bedetermined in the soil dust from open lot concen-trated cattle operations (OLCCO), then the nextstep is to investigate if these source specificmolecular markers are measurable in the airbornefugitive dust downwind from cattle operations.Should this also be the case, then the fraction ofambient aerosol derived from OLCCO can bedetermined.

ARTICLE IN PRESSW.F. Rogge et al. / Atmospheric Environment 40 (2006) 27–49 29

2. Experimental methods

2.1. Surface soil samples

The surface soil samples were collected according toEPA guidelines for surface and bulk materials byAshbaugh and coworkers (2003) as part of the SanJoaquin Valley Fugitive Dust Characterization Studyin 1997. The samples were taken next to theconcentrated cattle feeding operations, just outsidethe corral fence. Although portions of these sampleswere size-segregated via resuspension into PM10 andPM2.5 (Ashbaugh et al., 2003; Chow et al., 2003),only the surface soil samples were available to us foranalysis. The soil samples were shipped frozen over-night to our lab at FIU, where they were stored uponarrival in a freezer at less than �21 1C. The sampledescriptions and sampling locations are given inTable 1, for more details see Ashbaugh et al. (2003).

2.2. Extraction

For each sample, small rocks, if present, were firstremoved with a solvent rinsed stainless steel tweezers,and then the remaining soil was ground to powder. Asubsample of 5 g was selected for solvent extraction.A suite of internal standards, consisting of decanoic-d19 acid, tetradecanoic-d27 acid, n-eicosane-d42, n-tetracosane-d50, and n-triacontane-d62, was addedto each sample aliquot just before solvent extraction.Every 5 g sample was extracted three times, each with30mL dichloromethane using mild ultrasonicationfor 10min. The extracts were combined, filtered andconcentrated by rotary evaporator to about 3mL,then further to about 1mL using a stream of highpurity nitrogen. Each extract was split and onealiquot derivatized with diazomethane (preparedfrom 1-methyl-3-nitro-1-nitrosoguanidine in ether)to convert organic acids to their methyl esters. Fromthe same soil samples, independently, a second set

Table 1

Soil sample locations and descriptionsa

Sample ID Source Latitude L

FDCTD1 Dairy 3610701300 N 11

FDCTD2 Dairy 3613005400 N 11

FDCTF1 Feedlot 3513000200 N 11

FDCTF2 Feedlot 3611501000 N 12

OC: Organic carbon.aAshbaugh et al. (2003).bChow et al. (2003).

was extracted to examine exclusively the polarorganic compounds fraction. These were ultrasoni-cated three times for 10min with dichloromethane:-methanol (1:1; v/v). Aliquots of the total extractswere converted to trimethylsilyl derivatives byreaction with N,O-bis-(trimethylsilyl)trifluoroaceta-mide (BSTFA) containing 1% trimethylchlorosilaneand pyridine for 3 h at 70 1C.

2.3. Instrumental analysis

All sample extracts were analyzed by gas chro-matography–mass spectrometry (GC–MS). Themethylated extracts of the soils were analyzed usingan Agilent 6890 gas chromatograph interfaced withan Agilent 5973 MSD and equipped with a Grobinjector that was operated in the pulsed splitlessmode at 25 psi until 1.0min. The injector tempera-ture was set to 300 1C. A DB5-MS capillary column(30m� 0.25mm i.d. and film thickness of 0.25 mm, J& W Scientific, Rancho Cordova, California) wasused. The column temperature program consisted ofinjection at 60 1C and hold for 2min, temperatureincrease of 6 1Cmin�1 to 300 1C, followed by anisothermal hold at 300 1C for 15min. The MSD wasoperated in the electron impact (EI) mode with anionization energy of 70 eV. The scan range was setfrom 50 to 550 daltons. The underivatized and thesilylated total extracts were also analyzed with asecond Agilent GC–MS system (GC 6890,MSD5973), but using a DB1-MS capillary column.The MS and GC operating conditions were thesame as above.

2.4. Compound identification and quantification

Data were acquired and processed with the HP-Chemstation software. Individual compounds wereidentified by comparison of mass spectra withliterature and library data, comparison of mass

ongitude County OC (%) of PM10b

913101300 W Tulare 13.9

914300400 W Fresno 24.3

910603000 W Kern 12.7

011505300 W Fresno 22.9


spectra and GC retention times with authenticstandards and/or interpretation of mass spectro-metric fragmentation patterns. Relative ion countswere converted to compound mass using the areacounts of the internal recovery standards (fivedeuterated standards added to the samples beforeextraction). Relative response factors (RRFs) wereobtained by injection of external standards thatcontained the compound of interest, and 1-phenyl-dodecane as coinjection standard. Measurementuncertainty was determined using replicate solventextractions and GC/MS analyses and the standarddeviation (STD) of each of the RRFs obtained forauthentic standards.

For compounds for which no authentic standardswere available, the RRFs and measurement un-certainties were assumed to be identical to those ofavailable standard compounds with similar chemi-cal structures, polarities, and molecular weights.

3. Results and discussion

3.1. Environmental setting

Cattle confined in open lot dairies and beef cattlefeedlots can be a substantial source for fugitive dust.Fugitive dust emissions from OLCCO depend atleast on four major factors: (1) The size of thefeedlot or dairy farm, including number of cattle,and cattle density. Space allocated per head of cattledepends mainly on the annual total rainfall, withlower space requirements for arid regions. For openlot dairies the space allocated per head rangesfrom 50 to 120m2 and for feedlots from 7 to 40m2.(2) The daily temperature cycle and rainfallpotential indirectly control how long manuredroppings need to dry; this is mainly a function ofthe geographic location and climate. (3) Lot design,manure management, ground moisture control, andcleaning schedule. Typically the lots are paved on anincline to insure that the liquid portion of theexcrements can run off to a nearby wastewatertreatment facility. (4) The activity pattern of thecattle. For example, in a warm climate likeCalifornia, cattle emerge typically in the late after-noon from their lethargy and move around, causingmore dust from dried manure and soil to be kickedup in the early evening hours. With the tendency ofthe atmospheric temperature stratification to be-come more stable after sundown, dense dust cloudscan persist throughout the night until the earlymorning.

In the 1970s, Algeo et al. (1972) and Elam et al.(1971) determined the total suspended particulatematter (TSP) concentrations downwind of 25California feedlots during summer in the absenceof dust control measures. Daily peak concentrationswere typically observed after sundown between 7and 10 pm with TSP levels ranging from about 2000to 35,500 mgm�3 with an average peak concentra-tion of 14,200 mgm�3. Depending on fugitive dustcontrol practices, these very high concentrations canbe much lower, typically 10–30% of that with nodust control measures.

The particle size distribution of airborne dustfrom OLCCO has been determined by severalresearchers for different locations. The ratio ofPM10 to TSP ranges from 40% to 48.2% and theratio of PM2.5 to TSP ranges from 5% to 6%(ARB, 2003; OMNI, 1989; Sweeten et al., 1998).For the soil samples considered here, Chow andcoworkers (2003) obtained PM10 samples byresuspension of the original surface soil samplesand determined the OC content to range from12.7% to 24.3%, see also Table 1. Depending on thecorrection factor to estimate organic matter contentfrom these OC data, it can be assumed that about20–40% of the PM10 emitted from concentratedcattle operations consists of organic matter.

US-EPA emission factors for TSP and PM10 forfugitive dust from feedlot operations are availablefor dry season only; see AP-42, USEPA (1986).According to AP-42, 17.2 tons of PM10 is releasedto the atmosphere per 1000 head throughput. In afeedlot with 100,000 cattle at a time, where cattlestay 4–5 months for fattening, roughly 200,000cattle enter and leave the feedlot per year. Thisamounts to almost 3500 tons of PM10 emitted peryear for a feedlot designed to hold 100,000 head ofcattle at any time and in the absence of any fugitivedust control measures. Although this is an upperestimate for cattle PM10 contributions, it does notinclude any particulate emissions from farm vehiclesused for fodder, manure, and animal transport,feedstuff processing, and other tasks. Consequently,at such particulate matter emission rates, nearbytowns are likely to be impacted by organic dustfrom concentrated cattle operations.

3.2. Cattle diet and metabolism

The organic matter content of fugitive dustemissions from concentrated cattle operations aremainly related to the original diet and chemical


conversions in the digestive tract of cattle. Cattle areruminants and therefore have, unlike many otheranimals, a stomach with four compartments utiliz-ing specialized microorganisms for digestion of evenlow quality fodder. Therefore, feces from cattle is inmany ways chemically different from that of otheranimals raised in large farms such as pigs orchickens. Hence, a brief review on feedstuff andfeeding practice will help to aid in selecting uniqueorganic marker compounds for OLCCO.

Open lot dairy farms and feedlots are occupiedtypically by large numbers of cattle. In contrast topasture and open range cattle that feed on nativeplants by availability and preference, cattle inconcentrated cattle operations are subjected tofeeding strategies with the goal to enhance yieldand performance. For feedlots, the objective is tomaximize weight gain, while for dairy cows, tomaximize milk production. The volumetric capacityof the cattle’s gut for fodder places an upper limiton how much feedstuff can be consumed per day.The higher the content of forage and other fibrousfeed in the diet, the sooner the cattle needs to stopeating. By carefully selecting feed processing, therate and extent of digestion can be enhanced. Inmodern mass cattle feeding operations, the rumi-nant diet can consist of a great variety of feedstuffs,ranging from fresh, hay, or silage of a wide varietyof forages, processed grains, feed supplements suchas minerals, vitamins, fats (oilseeds and tallowblends), pharmaceuticals and others. In California,some of the major ruminant feeds include forages,particularly alfalfa, fresh or as hay or silage, andsorghum hay. Concentrate feedstuff can consist of acombination of the following fodder items: corn assilage, ground or as hominy; wheat as silage ormiddlings, or derived from other processing meth-ods; oats; barley; distillers dried grains, soybean,canola, cottonseed, sunflower meal (or other fatsources such beef tallow or pork lard); beet pulp;almond hulls; and others (e.g., Amaral-Philips andHemken, 1997; Drake et al., 2002; George et al.,2002; Getachew et al., 2004).

With the cattle droppings, undigested organiccompounds from the cattle fodder are continuouslyadded to the ground, leading to their overallenrichment in the top soil. Depending on theruminant diet, the organic composition in thesurface soil can vary, and with it, the compositionof fugitive dust from OLCCO. In general, the majororganic compounds found are derived from epicu-ticular waxes and internal (generally intracellular)

lipids of forages and grains. Some of thosecompounds are altered by microbial activity duringpassage through the digestive system of the cattle,and are discussed below. The concentration oforganic compounds in the surface soil samples fromthe dairies (FDCTD1 and FDCTD2) and feedlots(FDCTF1 and FDCTF2) are given in Table 2.

3.3. Aliphatic lipids

In the soil from open lot concentrated cattleoperations, undigested plant epicuticular wax con-stituents are comprised of n-alkanes XC27 with astrong odd carbon number predominance andcarbon number maximum (Cmax) at 31, n-alkanoicacids XC22 with a strong even carbon numberpredominance and Cmax at 30, and n-alkanols XC22

also with a strong even carbon number predomi-nance and Cmax at 30 (Table 2). An example of aGC-MS total ion current trace for a total methy-lated extract is shown in Fig. 1a. Epicuticular plantwax n-alkanes are chemically very stable and cantherefore be used to estimate the intake and dietcomposition for cattle and other herbivores (e.g.,Bugalho et al., 2004; Dove and Mayes, 1996).Comparing the content of undigested plant waxaliphatic lipids in the surface soils from the dairiesand feedlots, it is evident that forage is part of thecattle diet in both dairies (FDCTD1, FDCTD2) andalso at feedlot FDCTF2. In contrast, the soil dustsample from feedlot FDCTF1 contains markedlylower levels of plant derived epicuticular waxconstituents, suggesting that forage is only a minorcomponent of the cattle diet. Minor secondary lipidproducts are comprised of n-alkanals ranging frommainly C12 to C29 and n-alkan-2-ones ranging fromC11 to C35. From the vegetation feed, unaltered andhydrogenated intracellular lipids are found in thesurface soil dust samples and consist mainly of then-alkanoic and alkenoic acids oC20 with Cmax at18, steroids, triterpenols, chlorophyll breakdownproducts and various tocopherols (Table 2).

In forage- and cereal-based feed, as well as insupplemental fat sources such as canola, sunflower,soybean, and cottonseed, palmitic acid (C16) is themajor saturated fatty acid and therefore, commonlyfound at levels two to five times higher than stearicacid (C18) (e.g., Aurousseau et al., 2004; Chilliard etal., 2001; Collomb et al., 2004; Dhiman et al., 1999;Doreau and Poncet, 2000; Elgersma et al., 2003;French et al., 2003; Whiting et al., 2004). Incontrast, the sum of the unsaturated C18 fatty acids

ARTICLE IN PRESS

Table

2

Concentrationsoforganic

compoundsin

thesoilsamples(reported

asmg

g�1)a

Compounds

Form

ula

Dairies

Feedlots

CompdID

b

FDCTD1

FDCTD2

FDCTF1

FDCTF2

n-A

lkanes

n-Pentacosane

C25H

52

0.9370.03

0.3170.01

——

a

n-H

exacosane

C26H

54

0.2270.007

0.0670.002

——

a

n-H

eptacosane

C27H

56

5.470.23

1.970.08

0.2970.01

2.1070.09

a

n-O

ctacosane

C28H

58

1.270.03

0.4070.01

0.0770.003

0.6270.02

a

n-N

onacosane

C29H

60

35.170.99

11.670.33

1.670.05

12.570.36

a

n-Triacontane

C30H

62

2.970.09

1.170.03

0.1270.003

1.270.04

a

n-H

entriacontane

C31H

64

84.272.71

32.771.05

3.770.12

39.571.27

a

n-D

otriacontane

C32H

66

1.970.06

0.7370.02

0.1870.005

1.170.03

a

n-Tritriacontane

C33H

68

7.770.24

2.270.07

0.2470.008

3.370.11

a

n-A

lkanoic

aci

ds

n-O

ctanoic

acid

C8H

16O

20.5270.021

0.1070.004

0.0270.0008

0.0970.0037

a

n-N

onanoic

acid

C9H

18O

21.170.04

0.0470.0010

0.0170.0004

0.0970.0033

a

n-D

ecanoic

acid

C10H

20O

20.9070.034

0.0670.0020

0.0170.0004

0.1370.0049

a

n-U

ndecanoic

acid

C11H

22O

20.2570.009

0.0270.0007

0.0370.0010

0.0770.0024

a

n-D

odecanoic

acid(lauricacid)

C12H

24O

21.970.07

0.2470.0084

0.0870.0028

0.7470.026

a

n-Tridecanoic

acid

C13H

26O

21.170.04

0.170.0038

0.0270.0007

0.7670.029

a

n-Tetradecanoic

acid(m

yristic

acid)

C14H

28O

211.870.50

2.870.12

0.3770.0157

11.370.48

a

n-Pentadecanoic

acid

C15H

30O

29.170.43

2.770.13

0.2070.0095

8.970.42

a

n-H

exadecanoic

acid(palm

itic

acid)

C16H

32O

2101.074.9

83.974.1

4.570.22

134.576.5

a

n-H

eptadecanoic

acid

C17H

34O

29.770.52

6.570.35

0.4070.0215

16.770.90

a

n-O

ctadecanoic

acid(stearicacid)

C18H

36O

2219.6712.0

328.0717.9

13.970.76

391.0721.3

a

n-N

onadecanoic

acid

C19H

38O

21.170.07

0.9770.06

0.0970.0058

2.070.13

a

n-Eicosanoic

acid

C20H

40O

210.370.66

9.970.63

0.6070.0381

12.470.79

a

n-H

eneicosanoic

acid

C21H

42O

21.270.10

0.8670.07

0.1770.0147

1.570.13

a

n-D

ocosanoic

acid

C22H

44O

212.270.86

8.970.63

1.470.10

10.470.73

a

n-Tricosanoic

acid

C23H

46O

23.370.28

3.070.25

0.6770.056

4.770.39

a

n-Tetracosanoic

acid

C24H

48O

214.871.37

12.671.16

2.970.27

16.371.51

a

n-Pentacosanoic

acid

C25H

50O

21.770.20

1.870.21

0.3870.045

1.670.19

a

n-H

exacosanoic

acid

C26H

52O

28.671.06

7.270.89

2.370.28

8.170.99

a

n-H

eptacosanoic

acid

C27H

54O

21.370.19

0.8470.12

0.2670.037

0.6570.093

a

n-O

ctacosanoic

acid

C28H

56O

212.971.90

10.171.49

3.570.52

7.771.14

a

n-N

onacosanoic

acid

C29H

58O

25.670.79

4.170.58

1.070.14

2.370.32

a

n-Triacontanoic

acid

C30H

60O

256.678.1

57.578.2

12.371.76

32.174.6

a

n-H

entriacontanoic

acid

C31H

62O

22.670.35

1.970.25

0.5070.067

1.270.16

a

n-D

otriacontanoic

acid

C32H

64O

213.171.81

10.471.44

3.170.43

7.371.01

a

n-Tritiacontanoic

acid

C33H

66O

20.5570.08

0.3470.048

0.1570.021

0.2770.038

a

n-Tetratriacontanoic

acid

C34H

68O

21.770.24

1.470.19

0.5970.084

1.670.23

a

n-A

lken

oic

aci

ds

Octadecenoic

acids

C18H

34O

256.473.1

63.073.4

2.670.14

123.476.7

a

Octadecadienoic

acid

C18H

32O

224.071.3

27.271.5

0.6270.034

51.172.8

a

W.F. Rogge et al. / Atmospheric Environment 40 (2006) 27–4932

ARTICLE IN PRESSn-A

lkanols

n-O

ctadecanol

C18H

38O

2.670.09

0.8270.030

——

b

n-D

ocosanol

C22H

46O

5.670.21

2.270.081

0.4870.018

1.970.07

a

n-Tetracosanol

C24H

50O

13.270.69

4.170.21

1.270.062

6.570.34

b

n-H

exacosanol

C26H

54O

2.4170.13

1.970.10

1.470.073

2.770.14

b

n-O

ctacosanol

C28H

58O

6.3170.74

4.870.57

2.570.29

6.970.81

b

n-Triacontanol

C30H

62O

10.971.36

9.671.19

4.970.61

9.271.15

b

n-D

otriacontanol

C32H

66O

——

2.670.34

3.970.51

b

n-A

lkanals

n-D

odecanal

C12H

24O

0.1970.005

—0.1270.003

0.3370.009

a

n-Tridecanal

C13H

26O

0.3570.016

0.2170.097

0.1070.004

0.3470.016

a

n-Tetradecanal

C14H

28O

1.970.05

1.670.04

0.4270.012

3.070.08

a

n-Pentadecanal

C15H

30O

2.170.04

1.570.03

0.5670.011

3.570.07

b

n-H

exadecanal

C16H

32O

2.470.17

2.070.14

0.6270.044

2.470.17

b

n-H

eptadecanal

C17H

34O

0.5570.020

0.5270.0191

0.2070.007

0.5070.018

b

n-O

ctadecanal

C18H

36O

1.870.066

3.970.14

2.270.08

4.270.15

b

n-Eicosanal

C20H

40O

0.9670.049

3.370.17

1.670.08

2.570.13

b

n-H

eneicosanal

C21H

42O

——

0.1070.005

—b

n-D

ocosanal

C22H

44O

1.170.13

0.7770.090

0.6070.070

1.370.15

b

n-Tricosanal

C23H

46O

0.9770.12

0.2970.036

0.5070.062

0.8770.108

b

n-Tetracosanal

C24H

48O

1.970.25

0.8770.115

0.7470.098

1.770.22

b

n-Pentacosanal

C25H

50O

0.6070.081

0.2370.031

0.1070.014

0.4270.057

b

n-H

exacosanal

C26H

52O

1.570.21

0.6470.089

0.4870.067

0.7070.097

b

n-H

eptacosanal

C27H

54O

0.6270.088

0.6270.088

0.2770.038

—b

n-O

ctacosanal

C28H

56O

3.570.50

2.570.36

3.470.49

2.470.35

b

n-N

onacosanal

C29H

58O

0.7470.11

1.170.16

0.8070.116

—b

n-A

lkan-2

-ones

n-D

odecan-2-one

C12H

24O

——

—0.0370.0008

a

n-Tridecan-2-one

C13H

26O

0.0570.0013

0.0270.0052

0.0170.0003

0.2770.0070

a

n-Tetradecan-2-one

C14H

28O

0.0470.0014

0.0270.0068

—0.0970.0031

a

n-Pentadecan-2-one

C15H

30O

0.1370.0044

0.1070.0034

0.0170.0003

0.5070.017

a

n-H

exadecan-2-one

C16H

32O

0.0670.0016

0.0570.0014

—0.3870.010

b

n-H

eptadecan-2-one

C17H

34O

0.1270.0033

0.0870.0022

—0.2270.0061

b

n-H

eneicosan-2-one

C21H

42O

—0.0370.0092

——

b

n-Tricosan-2-one

C23H

46O

—0.0270.0006

——

b

n-Tetracosan-2-one

C24H

48O

—0.0270.0007

——

b

n-Pentacosan-2-one

C25H

50O

0.0670.0020

0.0370.0010

——

b

n-H

exacosan-2-one

C26H

52O

0.0370.0011

0.0270.0007

——

b

n-H

eptacosan-2-one

C27H

54O

0.2270.008

0.1270.0044

——

b

n-N

onacosan-2-one

C29H

58O

0.6370.024

0.3670.014

——

b

n-H

entriacontan-2-one

C31H

62O

1.770.07

1.470.05

——

b

n-D

otriacontan-2-one

C32H

64O

0.4470.017

0.4070.016

——

b

n-Tritriacontan-2-one

C33H

66O

1.270.05

1.070.042

——

b

n-Pentatriacontan-2-one

C35H

70O

0.2570.011

0.1970.0084

——

b

Ste

roid

s

Cholesterol(cholest-5-en-3b-ol)

C27H

46O

158.4718.2

143.8716.5

119.8713.7

458.0752.5

a

Cholestanol(5a-cholestan-3b-ol)

C27H

48O

44.975.4

25.573.1

16.171.9

55.076.6

a

Coprostanol(5b-cholestan-3b-ol)

C27H

48O

62.477.1

80.279.2

86.179.9

260.0729.8

a

epi-Coprostanol(5b-cholestan-3a-ol)

C27H

48O

84.179.9

120.1714.2

142.8716.9

341.7740.4

a

Ergosterol

C28H

44O

0.9170.109

0.7270.086

0.4670.055

0.3670.043

a

W.F. Rogge et al. / Atmospheric Environment 40 (2006) 27–49 33

ARTICLE IN PRESSTable

2(c

onti

nued

)

Compounds

Form

ula

Dairies

Feedlots

CompdID

b

FDCTD1

FDCTD2

FDCTF1

FDCTF2

Brassicasterol

C28H

46O

1.570.20

0.8470.110

0.1570.0197

0.8170.11

b

Ergostanol(24a-methyl-5a-cholestan-3b�

ol)

C28H

50O

53.777.7

36.975.3

27.273.9

113.1716.3

b

Campesterol

C28H

48O

40.675.0

34.674.3

29.173.6

79.479.9

a

5b-Campestanol(24a-methyl-5b-cholestan-3b-ol)c

C28H

52O

48.675.7

14.671.7

12.271.4

155.9718.4

b

epi-5b-Campestanol(24a-methyl-5b-cholestan-3a-ol)d

C28H

50O

64.177.9

24.773.1

40.575.0

138.1717.1

b

Stigmasterol(stigmasta-5,22-dien-3b-ol)

C29H

48O

16.872.1

19.272.4

17.372.2

33.374.2

a

Sitosterol

C29H

50O

75.4710.4

43.776.0

30.074.1

196.3727.1

a

5b-Stigmastanol(24b-ethyl-5b-cholestan-3b-ol)e

C29H

52O

71.2710.3

53.577.7

68.779.9

223.4732.3

b

epi-5b-Stigmastanol(24b-ethyl-5b-cholestan-3a-ol)f

C29H

52O

301.7744.3

225.8733.2

220.8732.4

722.37106.1

b

Stigmasta-7,16-dien-3b�

ol

C29H

48O

286.6740.3

57.578.1

52.977.4

334.4747.0

b

Stigmastanol(sitostanol)g

C29H

52O

165.9722.3

55.977.5

81.1710.9

225.4730.3

b

D7-Stigmasterol(5a-stigmast-7-en-3b-ol)

C29H

50O

98.4715.7

66.1710.6

31.175.0

38.176.1

b

Stigmasta-3,5-dien-7-one

C29H

46O

3.470.61

3.170.56

2.570.45

3.670.65

b

5b-Stigmastan-3-one

C29H

50O

12.871.9

7.471.1

5.870.85

11.071.6

b

5a-Stigmastan-3-one

C29H

50O

6.270.86

3.970.54

2.370.32

9.071.2

b

Tri

terp

enoid

s

a-Amyrin

C30H

50O

16.571.9

11.071.2

3.970.44

19.172.1

a

b-Amyrin

C30H

50O

8.971.01

6.970.78

2.370.26

10.271.2

a

Oleanonoic

acid(3-oxo-olean-12-en-28-oic

acid)

C30H

46O

31.970.26

6.070.83

--

b

Cycloartenol

C30H

50O

2.870.44

2.370.36

1.170.17

3.470.53

a

24-M

ethylenecycloartanol

C31H

52O

9.271.38

7.671.14

7.671.14

17.172.6

b

Isopre

noid

sand

Der

ivati

ves

Phytol

C20H

40O

26.072.2

25.372.1

1.570.13

23.972.0

a

Phytone

C18H

36O

2.770.23

0.7570.063

0.1670.013

1.070.08

a

Squalene

C30H

50

1.770.13

7.770.57

0.3870.028

4.570.33

a

Toco

pher

ols

and

der

ivati

ves

Vitamin

E(a-tocopherol)

C29H

50O

215.271.6

18.972.0

5.270.54

43.974.6

a

a-Tocopherylacetate

C31H

52O

36.970.76

8.170.89

0.1370.011

58.976.5

b

g-Tocopherol

C28H

48O

26.170.63

4.570.46

1.770.17

11.071.13

b

a-Tocopherolhydroquinone

C29H

52O

39.170.91

9.971.00

0.6570.69

35.673.6

b

aValues

notreported:below

detection.

bCompoundidentification:a,authenticstandard

verificationandquantification;b,MS-spectrum

verificationandquantified

usingauthenticstandard

withsimilarstructure,polarity,

andvolatility.Theindividualsample

resultsare

foundin

Rogge(2000).

c5b-Campestanol(24a-methyl-5b-cholestan-3b-ol)alsocalled

24-m

ethylcoprostanol.

depi-5b-Campestanol(24a-methyl-5b-cholestan-3a-ol)alsocalled

24-m

ethyl-epi-coprostanol.

e5b-Stigmastanol(24b-ethyl-5b-cholestan-3b-ol)alsocalled

5b-sitostanolor24-ethylcoprostanol.

f epi-5b-Stigmastanol(24b-ethyl-5b-cholestan-3a-ol)alsocalled

epi-5b-sitostanolor24-ethyl-epi-coprostanol.

gStigmastanol(sitostanol)alsocalled

24b-ethyl-5a-cholestan-3b-ol.


ARTICLE IN PRESS

Fig. 1. GC–MS total ion current (TIC) traces for feedlot soil extracts: (a) total methylated extract (FDCTF2); and (b) sterol range for

total silylated extract (FDCTF2) (numbers refer to carbon chain length of homologous compound series, n ¼ normal alkanes, � ¼ methyl

alkanoate, TAc ¼ a-tocopheryl acetate, THQ ¼ a-tocopherol hydroquinone, a- and b-A ¼ a- and b-amyrin, other compounds are

labeled).


(oleic acid, C18:1; linoleic acid, C18:2; linolenic acid,C18:3) is 10 to 20 times higher than the saturated C18

homologue (stearic acid) and also 5–10 times higherthan the respective C16 unsaturated fatty acid(palmitoleic acid, C16:1). Upon ingestion, forage-and cereal-based dietary fat as triglycerides is firstenzymatically lipolysed and a large portion of theunsaturated fatty acids are then hydrogenated bygut microorganisms in the forestomach of rumi-nants to the respective saturated analogues (Doreauand Ferlay, 1994; Moate et al., 2004; Polan et al.,1964). Because of the conversion of the unsaturatedto the saturated fatty acids, it is not surprising tofind that the major fatty acid in the surface soil

samples from OLCCO is stearic acid (C18), with aconcentration three times higher (3.070.7) thanpalmitic acid (C16). This is quite in contrast to thereversed higher C16 vs. C18 fatty acid ratio found inagricultural soils, plants, and other sources that mayrelease these two major fatty acids. Despite thehydrogenation of double bonds, mono- and diun-saturated C18 fatty acids are still detectable, butonly at about half the levels as found for stearicacid.

Isoprenoid derivatives, such as phytol (3,7,11,15-tetramethylhexadec-2-en-1-ol) and its oxidation pro-duct phytone (6,10,14-trimethylpentadecan-2-one) aredetectable as digestion products from the chlorophyll


in the green forage feed. These chlorophyll derivativesshow a similar trend as the epicuticular plant waxcompounds, with lowest concentrations as well forfeedlot FDCTF1. Squalene (2,6,10,15,19,23-hexam-ethyltetracosa-2,6,10,14,18,22-hexaene), the precursorin steroid biosynthesis, is present as a trace component(Table 2).

3.4. Tocopherols

Vitamin E, a natural antioxidant, is essential forgrowth, disease prevention, tissue integrity andreproduction in animal husbandry. Natural vitaminE, as it occurs in vegetation, consists primarily of a-tocopherol (I, R ¼ H, all chemical structures citedare given in Appendix I) with minor amounts of g-tocopherol (II) (e.g., Wyatt et al., 1998). Processedgrain-based cereal feed, hay, and ensiled forages aredeficient in vitamin E (McDowell et al., 1996; Yanget al., 2002). Thus, in contrast to pasture grazingcattle, concentrated cattle operations commonlysupplement the stock diets with vitamin E (e.g.,Arnold et al., 1992; Jensen et al., 1995; Lynch et al.,1999; McDowell et al., 1996; Wen et al., 1996). Thisresults in higher levels of a-tocopherol in animaltissues, which in turn increases tissue stabilitytoward lipid oxidation. Delaying lipid breakdownin cut beef also retards muscle-pigment oxidationand meat discoloration, and therefore, increases theshelf-life of fresh, frozen and vacuum-packed beef(e.g., Arnold et al., 1992; Jensen et al., 1995; Lynchet al., 1999; McDowell et al., 1996; Wen et al.,1996). Likewise, in order to maintain milk freshnessand pleasant flavor, vitamin E addition to thefeedstuff of milking cows in dairy farms is commonpractice (Focant et al., 1998; Havemose et al., 2004).Animal feed in concentrated cattle operations isnormally supplemented with a-tocopheryl acetate (I,R ¼ Ac), which is very stable to in vitro oxidationand is promptly hydrolyzed in the animal gut to a-tocopherol (e.g., Arnold et al., 1992; Jensen et al.,1995; Lynch et al., 1999; McDowell et al., 1996;Wen et al., 1996).

The dual origin of the tocopherols in these soilsamples is evident from the data shown in the keyion plot (Fig. 2a). The g-tocopherol is derivedexclusively from the vegetation feed, while a-tocopherol is derived from vegetation fodder andalso from the hydrolysis of the tocopheryl acetatefeed supplement. Excess a-tocopheryl acetate, nothydrogenated in the animal gut is detected as well inthe soil samples, varying from being the major

tocopheryl analog (feedlot FDCTF2, 58.9 mg g�1) tobeing the minor analog in soil dust from feedlotFDCTF1 (0.10 mg g�1), see Table 2. Because a-tocopheryl acetate is relatively stable, its presence inthe soil dust samples indicates the degree of usage ofa-tocopheryl acetate as feed supplement. A signifi-cant metabolite of a-tocopherol elutes after theacetate and the mass spectrum is shown in Fig. 2b.The molecular weight of 448 Dalton fits with thecomposition C29H52O3 and the fragmentation pat-tern is interpreted to be the hydration product of thechroman ring of a-tocopherol, namely 1-(20,50-dihydroxy-30,40,60-trimethylphenyl)-3-hydroxy-3,7,11,15-tetramethylhexadecane (a-tocopherol hy-droquinone, III). a-Tocopherol conversion anddegradation is complex. One route leads via hepaticoxidation to chroman ring opening, yielding a-tocopherol quinone which can then be reduced toa-tocopherol hydroquinone by microsomal andmitochondrial enzymes (Shi et al., 1999;Schmandke, 1964). In biological systems, a-toco-pherol hydroquinone is the most active antioxidantof the tocopherols (Liebler and Burr, 2000; Shiet al., 1999). Here, the highest a-tocopherol hydro-quinone concentration was found for feedlotFDCTF2, which also shows the highest levels ofall tocopherols and derivatives identified.

3.5. Steroids

What cholesterol (IV, R ¼ H) is for the animalkingdom, phytosterols are for plants. Today, morethan 100 different phytosterols are known (e.g.,Moreau et al., 2002). The most common phytosterolin terrestrial plants is sitosterol (IV, R ¼ bC2H5),followed by campesterol (IV, R ¼ aCH3), stigmas-terol (V, R ¼ bC2H5), brassicasterol (V, R ¼ bCH3)and others (e.g., Moreau et al., 2002; Hartmann,1998). Phytosterols are biosynthesized by themevalonate pathway, similar to cholesterol inanimals, and the synthesis proceeds via precursorsthat include squalene and cycloartenol (e.g.,Moreau et al., 2002; Venkatramesh et al., 2003).Phytosterols (carbon numbers: 28 or 29) are similarin structure to cholesterol (carbon number: 27).They have like most 4-desmethylsterols a doublebond between carbon 5 and 6 of the ring system andare thus called D5-sterols. Unlike cholesterol,phytosterols have an additional methyl or ethylgroup in the alkyl side chain at the C-24 positionand some (e.g., stigmasterol) a second double bondalso in the side chain.

ARTICLE IN PRESS

Fig. 2. (a) Key ion fragmentogram for m/z 416 and 430 for the tocopherols, and (b) mass spectrum of a-tocopherol hydroquinone.


In the animal gut, D5-sterols are biohydrogenatedby the gut microflora to their saturated stanolequivalents with possible configurational changes atthe C-5 and C-3 positions resulting in three isomers:stanols (5aH, 3bOH, VI), coprostanols (5bH,3bOH, VII) and epi-coprostanols (5bH, 3aOH,VIII) (Smith and Gouron, 1969; Grimalt et al.,1990; Leeming et al., 1997, 1998; Skurikhin, 1984;Snog-Kjaer et al., 1956). When excreted, stanols insoil are rather stable (Bull et al., 2000; Marvin et al.,2001); and therefore, used to identify ancient animalfarms (Evershed et al., 1997). The specificity of fecalsterols and stanols depends on the diet, sterolbiosynthesis by animals, and ability to biohydro-genate sterols to stanols by anaerobic bacteria in the

digestive tract (e.g., Leeming et al., 1996; Truong etal., 2003). Depending on the animals being carni-vores, herbivores, or omnivores, the sterol intakewith the food includes: (1) mainly cholesterol; or(2) mainly phytosterols; or (3) both, cholesterol andphytosterols. Consequently, the feces of carnivorousanimals include cholesterol, the 5b-derivativescoprostanol, epi-coprostanol and related isomers.Instead, the fecal steroids of herbivorous animalsinclude in addition to its own biosynthesizedcholesterol with the biohydrogenated derivatives,mainly 5a-phytosterols and 5b-phytostanols. Sitos-terol, the most common and stigmasterol the thirdmost common phytosterol, are both transformed bybiohydrogenation mainly to 5b-stigmastanol and


epi-5b-stigmastanol. Similarly, campesterol, thesecond most common phytosterol is transformedto 5b-campestanol and epi-5b-campestanol. Yeastsand many fungi also produce a 4-desmethylsterol,called ergosterol (IX, R ¼ bCH3) (Moreau et al.,2002), which is commonly associated with soilorganic matter and consequently with feedstuff.Ingested, ergosterol is also biohydrogenated to itsrespective 5b-stanol, ergostanol. Brassicasterol, an-other phytosterol, when biohydrogenated, is trans-formed as well in part to ergostanol (Moreau et al.,2002).

Large ruminant livestock such as cattle, consumea substantial amount of feed every day and produce

Fig. 3. GC–MS TIC traces for dairy farm soil extracts: (a) sterol rang

extract (FDCTD1) (numbers and abbreviations as in Fig. 1).

equally large amounts of dung. Thus, it is notsurprising, that the steroid mixture in these soil dustsamples from OLCCO is comprised of the originaland altered steroids ranging from C27 to C29

(Fig. 3a). Of all compound classes quantified, thesteroids are the most abundant compound group inthese soil samples, which is obvious in the examplesof the GC–MS chromatograms for the total extracts(e.g., Figs. 1a and 3b) and abundance (Table 2).Some of the isomers coelute in the underivatizedGC–MS analyses and thus are better resolved (alsowith better response factors) as the silylatedderivatives (Figs. 1b and 3b). The Kovats retentionindices are given in Table 3 for the free and silylated

e for total methylated extract (FDCTD1) and (b) total silylated


compounds. The primary (or precursor) steroids(e.g., Fig. 3a) are minor compared to the hydro-genated derivatives. Cholesterol ranges from 120 to458 mg g�1, campesterol from 29 to 80 mg g�1 andsitosterol from 44 to 196 mg g�1 (Table 2). Thesevalues are very high compared to uncontaminatednatural sediments and crop fields, where cholesterolor sitosterol are generally o1 mg g�1 (e.g., Chan etal., 1998; Rogge et al., 2006; Seguel et al., 2001).

The coprostanols and epi-coprostanols are thedominant isomers, with the stanols at lower levels(e.g., Figs. 1 and 2). The coprostanols and epi-coprostanols are poorly resolved by GC as theunderivatized compounds but resolve as the TMSethers (Table 3). The major compound is the C29

epi-stanol and therefore the mass spectrum of epi-5b-stigmastanol (VIII, R ¼ bC2H5, 24-ethyl-epi-coprostanol) is given in Fig. 4a. Its molecularweight is at m/z 416 and fragmentation occurs byloss of CH3 to m/z 401, loss of H2O to m/z 398 anda base peak at m/z 215. This 5b-series, as well as the5a-stanols (VI, 5aH), is illustrated in Fig. 4c usingthe base peak as key ion. Epi-5b-stigmastanol hasthe highest concentrations, ranging from 221 to722 mg g�1, with cholesterol (120–458 mg g�1) andepi-coprostanol (84–342 mg g�1) as next most abun-dant (Table 2). The mass spectrum of epi-5b-stigmastanol trimethylsilyl ether (VIII, R ¼ bC2H5,OTMS) is shown in Fig. 4b. Its molecular weight isat m/z 488 and fragments by loss of CH3 to m/z

473, loss of trimethylsilanol to the base peak m/z

Table 3

Kovats retention indices for C27–C29 sterols

Compound Co

Coprostanone (5b-cholestan-3-one)a C27

Coprostanol (5b-cholestan-3b-ol)a C27

epi-Coprostanol (5b-cholestan-3a-ol)a C27

Cholesterol (cholest-5-en-3b-ol)a C27

epi-Cholestanol (5a-cholestan-3a-ol)a C27

Cholestanol (5a-cholestan-3b-ol)a C27

5b-Campestanol (24a-methyl-5b-cholestan-3b-ol) C28

epi-5b-Campestanol (24a-methyl-5b-cholestan-3a-ol) C28

Campesterol (24a-methylcholest-5-en-3b-ol)a C28

5b-Stigmastanol (24b-ethyl-5b-cholestan-3b-ol) C29

epi-5b-Stigmastanol (24b-ethyl-5b-cholestan-3a-ol) C29

Ergostanol (24a-methyl-5a-cholestan-3b-ol) C28

Sitosterol (24b-ethylcholest-5-en-3b-ol)a C29

Stigmastanol (24b-ethyl-5a-cholestan-3b-ol) C29

aConfirmed with authentic standard.

398 and further fragmentation to yield the key ionat m/z 215. The trimethylsilyl ether of 24-ethylco-prostanol (VII, R ¼ bC2H5) elutes just prior to epi-5b-stigmastanol-TMS and also has a key ion at m/z

215. Therefore, the series is shown again in Fig. 4das the TMS derivatives and the isomers are labeled.

Stanones (X) and coprostanones (XI) are minorcomponents (Table 2), comprised maily of 5a-stigma-stan-3-one and 5b-stigmastan-3-one. In the case ofdomestic sewage outfalls, coprostanone (5a(H)-chole-stan-3-one) has been shown to be the major fecalsteroid (Grimalt et al., 1990). This is, however, not thecase for raw sewage or soil from feedlots and dairieswhere the coprostanones are minor.

3.6. Triterpenoids

The triterpenoids found in these surface soilsfrom open lot dairies and feedlots are minor inconcentration and consist of the unaltered naturalproducts derived from the feed. There are twocompound groups associated with triterpenoids.The first consisting of amyrins, a-amyrin (urs-12-en-3b-ol, XII), b-amyrin (olean-12-en-3b-ol, XIII)and a trace amount of oleanonoic acid (3-oxo-olean-12-en-28-oic acid), and the second of 24-methylenecycloartanol (XIV) and cycloartenol (XV)(Table 2). These compounds are quite common inmost vegetation (Simoneit, 1986, 1989) and thus arenot source specific for fugitive dust from animalhusbandry.

mposition Kovats index (DB-5)

Free compound As TMS ether

H46O 3057 —

H48O 3193 3002

H48O 3203 3016

H46O 3230 3098

H48O 3235 3010

H48O 3250 3104

H50O 3270 3107

H50O 3284 3113

H48O 3309 3204

H52O 3366 3196

H52O 3372 3206

H50O 3362 3216

H50O 3392 3296

H52O 3415 3305

ARTICLE IN PRESS

Fig. 4. Mass spectra of (a) epi-5b-stigmastanol and (b) epi-5b-stigmastanol trimethylsilyl ether, and key ion fragmentograms of m/z 215

for (c) the stanol range of the total methylated extract of FDCTD2 and (d) the same range for the total silylated extract.


4. Organic marker compounds

Determining the contribution of fugitive dustfrom OLCCO to the atmospheric particle burdenhas at best been speculative, especially whenconsidering the daily and seasonal variations indust emissions, controlled by a multitude of factors.If on the other hand suitable organic markercompounds were available for fugitive dust emis-sions from OLCCO, then it would be possible todetermine the actual contributions to a given site ofinterest. For an organic compound to be suitable asmarker: (1) the emissions should be high enough sothat it can be measured in the atmosphere overappreciable distances; (2) it should be chemicallystable so that it is not depleted significantly duringatmospheric transport from the source to thereceptor site; (3) it should be unique for the sourceof interest, if not unique; then (4) a set ofcompounds should reveal a source specific concen-tration pattern that is unique; and (5) it should beassociated with the particle size fraction underconsideration. Based on these conditions, possiblecandidates for organic markers of fugitive dustassociated with surface soil from OLCCO are: the

ratio of C18/C16 n-alkanoic acids, tocopherols andderivatives, phytosterols and phytostanols. Theseare examined next to assess their source specificityand suitability for source/receptor apportionmentstudies.

For a given diet and large number of animals,cattle dung is a more or less homogeneous material.Because dried cattle dung is pulverized by themilling action of cattle, fine as well as coarseparticulate matter contains the same organic andinorganic matter. Therefore, potential organicmarkers, derived here from surface soil samplescontaining dried cattle feces, are likely present inairborne fugitive dust from OLCCO.

4.1. Aliphatic lipids

The aliphatic lipids that are associated with thesurface soils at OLCCO are derived from undigestedepicuticular plant waxes and intracellular plantmatter. Lipids associated with epicuticular plantwaxes are also released directly to the atmosphereby abrasion of waxy protrusions from leaves (Roggeet al., 1993c), as well as from windblown dust fromagricultural fields (Rogge, 1999; Rogge et al., 2006).


The most prominent intracellular aliphatic lipids arepalmitic acid (C16), stearic acid (C18), and theirunsaturated homologues. As discussed before, theratio of stearic acid (C18) to palmitic acid (C16) isunique. In Fig. 5, the C18/C16 fatty acid ratio isshown for the surface soils from the dairy farms andfeedlots investigated here, and for other importantsources of particulate matter. The surface dustsfrom OLCCO show an average C18/C16 fatty acidratio of 3.0, while all other sources for particulatematter have C18/C16 ratios ranging from 0.17 to0.71, depending on source type. Consequently, atleast in the vicinity of OLCCO, the ratio for C18/C16

fatty acids can be used, both as a qualitative andquantitative tool to determine the spread of thefugitive dust plume, fall-out of fugitive dust, as wellas for source/receptor modeling studies. In countrieswhere cattle dung is used for cooking purposes, fineparticulate smoke from the combustion of driedcattle dung also has the characteristically elevatedC18/C16 fatty acid ratio, see Fig. 5 (Sheesley et al.,2003). Consequently, the ratio of C18/C16 fatty acidcan also be used as marker and indicator in areaswere cattle dung is burned for domestic purposes.

Fat

ty A

cids

Rat

io =

C18

/C16

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Dai

ries

& F

eedl

ots

Cot

ton

Fie

lds

(a)

Saf

flow

er F

ield

s (a

)

Tom

ato

Fie

lds

(a)

Alm

ond

Orc

hard

s (a

)

Vin

eyar

ds (

a)

Pav

ed R

oad

Dus

t (S

JV)

(a)

Unp

aved

Roa

d D

ust (

SJV

) (a

)

Cat

tle D

ung

Sm

oke

(b)

Pav

ed R

oad

Dus

t (LA

) (c

)

Surface Soil and Dust Samples

Fig. 5. Fatty acid ratio ¼ C18/C16 in surface soils of open lot dairies

unpaved roads, and in PM2.5 of many urban and rural sources. (a) Rog

(d) Hays et al. (2002); (e) Rogge et al. (1993c); (f) Rogge et al. (1991); (g

(j) Rogge et al. (1998); (k) Schauer et al. (2001); (m) Rogge et al. (1993

4.2. Tocopherols

Natural tocopherols have also been found insurface soils from fields growing different crops(Rogge, 1999; Rogge et al., 2006). Because toco-pherols are antioxidants they can degrade quickly.However, excess synthetic a-tocopheryl acetate thatis fed to cattle has not been found in other sourcesfor fugitive dust. But the tocopherol concentrationsin surface soils of OLCCO are typically low andvariable. Thus, only the more stable a-tocopherylacetate may be suitable to examine the spread andout-fall of fugitive dust from OLCCO.

4.3. Sterols and stanols

Sterols and especially their hydrogenated stanolsare chemically quite stable and therefore, arefrequently used as markers to differentiate sewagespills into surface waters from human sources(mainly coprostanol) and herbivores (mainly 5b-stigmastanol and epi-5b-stigmastanol) (e.g., Elhm-mali et al., 2000; Isobe et al., 2002; Leeming et al.,1996; Standley et al., 2000), in archeology (Evershed

Fol

iar

Veg

etat

ion

Sm

oke

(d)

Wax

y Le

af S

urfa

ce A

bras

ions

(e)

Ham

burg

er C

harb

roili

ng (

f)

Ham

burg

er C

harb

roili

ng (

g)

Stir

fryi

ng V

eget

able

s in

Oils

(h)

Stir

fryi

ng V

eget

able

s in

Oils

(i)

Woo

d S

mok

e (j)

Woo

d S

mok

e (k

)

Car

Exh

aust

(l)

Die

sel T

ruck

s E

xhau

st (

l)PM 2.5

and beef cattle feedlots, agricultural fields, dust from paved and

ge et al. (2006); (b) Sheesley et al. (2003); (c) Rogge et al. (1993b);

) Schauer et al. (1999), (h) Rogge (1999); (i) Schauer et al. (2002);

a).


et al., 1997), and long-term field studies (e.g., Bull etal., 2000). While it is unlikely that natural surfacewaters are a source for airborne fecal sterols andstanols, Radke and Herrmann (2003) found themassociated with airborne particulate matter abovean aeration tank in a sewage treatment facility.Land used for agriculture, especially during andafter harvesting, is a source for fugitive dust in theSan Joaquin Valley. Although animal steroids, suchas cholesterol and cholestanol, are found in mostagricultural soils, they are typically three-orders ofmagnitude higher in the surface soils from dairyfarms and feedlots (Rogge et al., 2006), see Fig. 6.Because meat cooking is a major source for airborneparticulate cholesterol emissions (Rogge et al.,1991), cholesterol is not suitable as markerfor fugitive dust emissions from open lot dairies

(a)

(b)

0.0

0.5

1.0

1.5

2.0

2.5

Cholesterol Cholestanol Coprostanol epi-Coprostanol

Sito

mg

/g o

f S

urf

ace

So

il

Open Lot Concentrated Cattle Operation

0

50

100

150

200

250

300

350

400

Cholesterol Cholestanol Coprostanol epi-Coprostanol

Sitos

mg

/g o

f S

urf

ace

So

il

Fig. 6. Concentrations of individual steroids in surface soils from (a) op

the San Joaquin Valley, CA.

and cattle feeding operations. Phytosterols suchas sitosterol, campesterol, and stigmasterol areubiquitous in the plant kingdom. They are foundin plant matter and consequently as well in soilfrom agricultural fields. The phytosterol concentra-tions measured in the surface soils of OLCCOare 80–100 times higher than what was found formost agricultural fields, except for surface soilsfrom almond orchards which have much higherlevels, but still the levels for OLCCO are two tofive times higher than those. Other sources forairborne particulate matter that are potentialphytosterol emitters are particulate leaf surfaceabrasion products (Rogge et al., 1993c; Simoneit,1989), cigarette smoking (Rogge et al., 1994),smoke from foliar burning (Oros and Simoneit,2001a, b; Hays et al., 2002), wood burning

sterol Stigmasterol Campesterol 5 -Stigmastanol

epi-5 -Stigmastanol

Cotton Fields (12)

Vineyards (3)

Safflower Fields (3)

Tomato Fields (5)

Paved & Unpaved Roads (9)

s: Dairies (2) and Feedlots (2)

terol Stigmasterol Campesterol 5 -Stigmastanol

epi-5 -Stigmastanol

en lot dairies and beef cattle feedlots; and (b) agricultural fields for


smoke (Rogge et al., 1998; Schauer et al., 2001),as well as wild fires. Consequently, by itself,phytosterols are not source specific for fugitivedust from OLCCO but may still be usable fornear source fall-out and plume dispersiondetermination.

In contrast, phytostanols such as 5b-stigmastanol(VII, R ¼ bC2H5) and epi-5b-stigmastanol (VIII,R ¼ bC2H5), the compounds with the highestconcentrations found in surface soils from OLCCO,are not detectable in surface soils from agriculturalfields (see Fig. 6) or any other source type thatrelates to biomass and emits particulate matter tothe atmosphere. These 5b-phytostanols are found insurface waters contaminated with waste fromanimal farms (Leeming et al., 1996; Standleyet al., 2000). Moreover, phytostanols are chemicallyeven more stable than their parent phytosterols(Bull et al., 2000). Consequently, 5b-stigmastanoland epi-5b-stigmastanol are the best potentialorganic marker compounds for fugitive dust emis-sions from OLCCO. Furthermore, smoke fromburning of dried cattle dung has also been foundto contain 5b-phytostanols (Sheesley et al., 2003). InAfrica and South Asia, where dried cattle dung isused as fuel, and where OLCCO are not typical,phytostanols can be used as organic markers forsmoke from burning dried dung.

Currently only limited information is available onthe contributions of particulate matter from aera-tion tanks of wastewater treatment tanks (Radkeand Herrmann, 2003). Therefore, should aerosolemissions occur from sewage treatment aerationtanks near a site considered for source apportion-ment of airborne particulate matter, then 5b-stigmastanol and epi-5b-stigmastanol should beused in conjunction with the following additionalsteroids: coprostanol (VII, R ¼ H), epi-coprostanol(VIII, R ¼ H), cholesterol (IV, R ¼ H), cholestanol(VI, R ¼ H), stigmastanol (VI, R ¼ bC2H5), andsitosterol (IV, R ¼ bC2H5).

5. Conclusions

Open lot dairy farms and beef cattle feedlots areconsidered to be an important source for fugitive

dust emissions in the San Joaquin Valley ofCalifornia. The organic compound composition ofsurface soils from two open lot dairy farms and twobeef feedlots has been studied by GC–MS. Morethan 100 individual compounds were quantified,including n-alkanes, n-alkanoic acids, n-alkenoicacids, n-alkanols, n-alkanals, n-alkan-2-ones, ster-oids, triterpenoids, isoprenoids, tocopherols, andothers. Some of the more abundant compoundsidentified in the surface soils include sterols, longchain n-alkanes and n-alkanoic acids from plantwax, and palmitic and stearic acid. Of particularinterest are organic compounds derived from fodderthat are biohydrogenated in the rumen of cattle. Themost promising marker compounds for fugitive dustfrom open lot dairy farms and cattle feedlots arederived from the biohydrogenation of phytosterolsin feed. Here, suitable marker compounds have beenidentified and verified in relation to other sourceprofiles. It has been found, that 5b-stigmastanol andepi-5b-stigmastanol are unique markers. In addi-tion, the ratio of C18/C16 fatty acids in surface soilsfrom open lot concentrated cattle operations ismarkedly higher (3.070.7) than for all otherpotential sources (average: 0.17–0.71). Further-more, antioxidant feed supplements (vitamin Eproducts) are also detectable in the surface soilsand the more stable synthetic a-tocopheryl acetate isa supporting source marker were supplementalvitamin E in form of a-tocopheryl acetate is fed tocattle.

Acknowledgements

This research was supported by the California AirResources Board under Agreement 98-3PM.P.M.M. thanks CNPq (Brazilian National ResearchCouncil) for financial support (No. 200330/01-2).

Appendix I

Chemical structures cited in the text are given asfollows:


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