ECOLOGICAL EXPOSURE AND EFFECTS OF AIRBORNE TOXIC CHEMICALS: AN OVERVIEW

edited by

1ThomasJ. Moser, 1 Jerry R. Barker, and 2David T. Tingey

1ManTech Environmental Technology, Inc.

2US Environmental Protection Agency

Environmental Research Laboratory 200 S.W. 35th Street Corvallis, Oregon 97333

NOTICE PB91-148460 ·



### EPA/600/3-91/001 January 

### 1991

The information in this document has been funded wholly (or In part) bythe U.S. Environmental Protection Agency. It has been subjected tothe Agency's peer and administrativereview, and It has been approved for publicat:on as an EPA document Mention cltrade names orcommercial products does

### not constitute endorsement of recommendation for use.

REPRODUCEDBY U.S. DEPARTMENTOF COMMERCE NATIONALTECHNICAL INFORMATIONSERVICE SPRINGFIELD,VA 22161TECHNICALREPORT

**~ATA** (l'laMrndllllll'ktriotuon thernme {oneomple 1.fUI'OfiiT NO. 

## 12. j:a. 

### PB91-1.ii8460

EPA/600/3-91/001
•.TITLE ANDIUITITLE [I. ,_1.\P'O"T DATE 

### January 1991 Ecological Exposure and Effects of jLPE"FORMINOO"OANIZATIONCODE 

### Airborne Toxic Chemicals: An Overview 7.AUTMOfUSI 

### II·••"'o"MINOo"oANIZATION "E"O"'TNo. 

### Thomas J. Moser, Jerry R. Barker, and David T. Tingey ji.P'UIFO"MINGO"GANIZATIONNAME ANOADOflUS 10.I'"OOflAIIotELEMENTNO. 

### 1st two, NSI, ERL-Corvallis; Tingey, 

## us EPA, ERL-Corvallis r11.eoN ""'"',,

.."

..NTNo.

12.I"ONSOfiiiNGAGENCY NAME ANOAOOfliSS 1a.TYPEOFREP'OflTANDP'EfliOOCOVEfliED



### US Environmental Protection Agency Pnhl;-::ho:>n 'D 

### Environmental Research Laboratory 1••PONSO"INGAGENCYCODE 

### 200 SW 35th Street EPA/600/2 Corvallis, OR 97333 11.

**I~''"LEMENTAfiiY** NOTES 

### 1990. 

## u.s. Environmental Protection Agency, Environmental Research Laboratory, Corvallis, OR. 16.Aa5Tfii-'CT


### Since the release of the Environmental Protection Agency's (EPA's) toxic release inventory (TRI) estimates for 1987, there has been a heightened concern over the nation's air quality. Primarily, this concern has been directed at human health effects in industrial-urban areas. The fact that many airborne chemicals pose hazards to human health is only one aspect of the problem. The continued deposition of airborne toxic chemicals pose threats to both terrestrial and aquatic ecosystems, this discussion is limited to terrestrial vegetation.

# <

-

**~7.** ICEY WOflDSANDDOCUMENTANALYSIS 

### Ia. DlSCRIPTOflS b.IDENTIFIERS/OPENINDIOTERMS c. COIATI

**field/Grou~**

11.O>STI'IIIUTIONSTATEMENT

**t1tfrl~fiiiTY.**

# f

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# :J('17til.eport} 21.NO.OF PAGES 

### nc ass1 1e 170 

### Release to Public 20.SECUfliTYCLASS (fJtU

**~~** 

## 22

.....1CE 

### Unclassified
&PA ,..,...auo-t ,.. 7JlTABLE OF CONTENTS

Table of Contents Preface Atmospheric Transport ofToxic Chemicals and Their Potential Impacts onTerrestrial Vegetation: An Overview (Thomas J. Moser, JerryR. Barker, and DavidT. Tingey) Organochlorines and Polycyclic Aromatic Compounds In the High Arctic (Grag W. Patton and Terry F. Bidleman) Air-Sea Exchange of Hexachlorocyclohexane in tr.e Bering and Chukchi Seas (Daniel A. Hinckley, Terry F. Bidleman, and Clifford P. Rice) Trace Metal Deposition and Cycling in Forested Ecosystems (AndrewJ. Friedland) Atmospheric Deposition ofTrace Metalsto Lichens and Effects ofTrace Metals 

### on Uchens (Thomas H. Nash Ill) Fate and Effects of PAHs in the Terrestrial Environment: An Overview (Nelson T. Edwards) Effects of Organic Chemicals in the Atmosphere on Terrestrial Plants (Jeffrey R. Foster) Effects ofAtmospheric Pollutants on Peatlands (Noel R. Urban) Use ofthe PHYTOTOX Database to Estimatethe Influence of Herbicide Drift on Natural Habitats in Agroecosystems (James E. Nellessen and John S. Fletcher) Biological Markers In Environmental Sentinels to Establish Exposure to, and Effects of, Atmospheric Toxicants (John F. McCarthy and Timothy J. Tschaplinski) AirToxics Ecological Effects Research Recommendations (Noel R. Urban and Jerry R. Barker) References

ii ii iii

8
20

32 40

48

60

90 102
107
128

130EFFECTS OF ORGANIC CHEMICALS IN THE ATMOSPHERE ON TERRESTRIAL PLANTS

INTRODUCTION Jeffrey R. Foster

**H~~bR~rehlnR~~e** Butler University Indianapolis, IN

Thousands of organic compounds are released intothe atmosphere each year by human activity. 

### Ofthese, the U.S. Environmental Protection Agency (EPA) has classified 328 as Priority

**P~lutants,** 

### based on scientific evidence oftoxicity In humans and other animals. However, onlytwo, benzene and vinyl chloride, have National Ambient Air Quality Standards. UntU recently, our knowledge of environmental releases ofthese substances was sketchy. In 1986, Congress passed the Emergency Planning and Community

**Right-t~Know**

### Act, requiring manufacturers of Priority

**P~l~nts** to report the amounts of each that they released, deliberately oraccidentally, intoair, water, and soil. The results 

### of the first round oftheToxic Release 

### Inventory (TRI) revealed that 865,000 metrictons of toxic organic compounds were released to

### the atmosphere in 1987 

### (US EPA. 1989). Small manufacturers (<3,400 kgjyear) and end users (e.g., farmers applying pesticides) were not required to report, and noattempt was madeto incorporate emissionsfrom area sources (dry cleaners, motor vehicle 

### exhausts, etc.). Thus, total emissions were probably 88Y8I8I times largerthan

### theTRI 

### data Indicate.
Following emission, organicsare dispersedwidely

### In the environment long-distance 

### transport occurs primarly In runoff, groundwater, and

### the atmosphere 

### (Cohen, 1986). 

### The latter pathway hasspread organicsto

### the most remote 

### regions of

### the globe (Schroederand Lane, 1988). Chlorinated pesticides such as DDT, lindane, dieldrin, 

### and hexachlorobenzene (HCB) arethe

### bestknown examples. having been detected 

### in inorganic media and organismsas distantfrom emissions
60

### as theArctic 

### and Antarctic (Atlas and Giam, 1981;

### Tanabe 

### at al.• 

### 1983; 

### Gregorand 

### Gummer, 1989). 

### Long-<jistance dispersal d nonpesticide organics, Including polycyclic aromatic hydrocarbons (PAHs). polychlorinated biphenyls (PCBs), chlorophenols, and 

### alkanes, 

### has also been

### demonstrated (Lunde and Bjorseth, 19n; 

### Heit et 

### al., 1984; 

### PaasMrta et

### al., 

### 1985; 

### Wickstrom and Tolonen, 1987; 

### Gregor and 

### Gummer, 1989).


### What are

### the

## consequences d this global 

### organic contaminant

### load 

## on the 

### structure and 

### function d organisms and natural ecosystems?

PROBLEM STATEMENT

Avast amount of

### literature has been accumulated on 

### the ecotoxlcology d organics In natural environments. However, it is 

### quite clearthat

### thedrivingforce for research has been the 

### concern over their accumulation In crops for human or livestockconsumption, primarily as residues following pesticide applications, and in accumulation 

### via biomagnlficatlon upaquatic and terrestrial food 

### chains to organisms that are consumed by humans (e.g., fish), 

### or organisms that bring 

## us aesthetic pleasure (e.g., birds). There is, 

### comparatively, asevere dearth d information concerning the

### fate and effects 

### d toxic organics in noncrop, terrestrial, vascular plants.


### The only comprehensive assessment d the 

### literature 

## on organic chemicals and terrestrial plants is

### the EPA-funded PHYTOTOX computer database (Fletcheret al., 1988). 

### This database contains 

### n,825dose-response (effects) 

### records gleaned from 9,700 

### bibliographic references published between 1926

### and 1984. Of

### the 1,569 

### species represented In 

### PHYTOTOX. only 417

### are native species 

### growing in natural habitats. 

### The latter

### value Increases to

### 557 Ifold-field-succession species are included. Together, wlld-grOYm and old-field species constitute 4,524 

### records, or5.8%

### d the

### total database. Thus, the existing 

### literature is 

### heavly oriented toward agronomic species. 

### Pesticides constitute 21% 

### d all 

### PHYTOTOX effects 

### records. Infact. 

### cithe 

### 20 most 

### often cited 

### chemicals, only two (both hormones) 

### are 

### not pesticides. 

### And, 

## cny4.71E. d records 

### are 

### for native plants 

### growing in natural environments.
From the

### toxicological standpointalone, 

### I 

### Is evidentthat 

### lnsufficiet"lt data

### existfor EPAto undertake risk 

### analyses

### for the 

### effects 

### d organics on natural terrestrial vegetation. 

### In a:klition, 

### litUe is 

### known 

### concerning deposition rates 

### d organicsto

### terrestrial ecosystems, rates d plant uptake, and subsequent translocation and 

### metabolism.



### 61The objectives 

### d 

### this report are to: (1) discuss 

### mechanisms 

### d 

### atmospheric deposition of organic substancesto

### t•arrestrial vegetation; 

### (2) describe probable 

### pathways 

### d terrestrial vascular plant uptake 

### d organics; 

### (3) summarize 

### existing literature 

### on 

### the effects 

### d organics 

### onterrestrial vascular plant growth and 

### physiological processes; 

### (4) specuate on 

### potential, as yet unstudied, 

### effects; and 

### (5) recommend areas forfuture research.



### I rely heavly

## on the herbicide literature, which greatly exceeds thatforall 

### otherorganics combined, 

### but make

## no claim to provide any 

### but the most

### cursory

## overview. i wll consider all kinds 

### d airborne organics, with

### the exceptions of

### peroxyacetyl nitrate 

### (PAN), 

### a 

### lcnaNn gaseous oxidant and phytotoxinthat 

### has received much attention during

### the last 20 

### years (see Mudd, 1975,

### for a 

### review), and the chlorofluorocarbons. Also, 

### IY'tll 

### not reviewthe effects 

### d water-borne organics 

### on aquatic macrophytes.

CONCEPTUAL APPROACH
Figure 1 shows 

### a model 

### ofthe various fluxes 

### of airborne organic substances onto, Into, and through terrestrial vascular plants. Fluxes 

### specific to

### the canopy are 

### shown In detal In Figure 

### 2. In the discussion thatfollows, 

### I will deaf with most

### d thesefluxes, with the exception 

### d within-soil fluxes, which are beyond

### tt-.e scope c:lthis paper. Following 

### that, I wll describe 

### known effects of organics on terrestrial plants, and finish with recommendations for future research.

ATMOSPHERIC DEPOSITION Atmospheric Occurrence
Organics enter the atmosphere primarily In gaseous or particulate form. Initial mixing In the air leads to partitioning between

### thevapor, solid, and liquid phases (Schroeder and Lane, 1988). Phase distributions are determined by inherent chemical properties, Includingvapor pressures, Henry's Law constants 

### (H. equlibrium ratio 

### d the concentration 

### In air

### to concentration 

### In water), diffusion coefficients in air and water, and equilibrium constants 

### (pK.; forweak acids) (Tucker and Preston, 1984; Mackay et al., 1986; Bidleman, 1988; Ugocld and Pankow, 1989). Organics enter precipitation bydissolving directlyfrom

### the vapor phase Intowater droplets and by being physically scavenged as aerosols byfalling droplets. 

### The 

### -washout ratio•

### fN; mass 

### d organics 

### per unit volumed rain divided by mass 

### d organics 

### per unitvolume 

### d air) describes

### the net 

### effect 

### d 

### these processes (Bidleman, 1988).



### 62

### wet&dry deposition

•elatiiiUIIOII



### adsorption wet&dry 

### deposition

translocation & 

### detoxification

# d~~~~iion<::=

# ~--->

# un'fl~~ated biological

# r:/' II rootuptake

# ~ degradation 

# {!, "-.... root exudation

leaching



# ------ 

# --- watertable

FJGURE 1. Conceptual model 

### d fluxes 

### d airborne organics toand within terrestrial 

### ecosystems.



### 63

### wet deposition

wastioff stomatal absorption 

### cuticle absorption/ IMfsorption surface moisture absorption



# I resuspension volatilization photodecomposition

FIGURE 2. 

### Same as Fig. 1, 

### but 

### enlarged to 

### showfluxes associated with 

### leaves.

64Compared tothe ma!orair pollutants (ozone, sulfur dioxide, nitrogen dioxide, carbon monoxide), air concentrations of organics are 

### not well-characterized. A great variety have been detected whenever and wherever they have been looked for. Urban air contains hundreds 

### of volatile organic compounds (VOCs) from industrial emissions, motorvehicle exhausts, and other anthropogenic sources {Atlas and Giam, 1988; Bruckmann

### et al., 1988; Shah and Singh, 1988; Edgerton et al., 1989). Some VOCs are secondary products

### ofthe photochemical reactions that produce smog (e.g., nltrophenols [Nojima and Kanno, 1977)). 

### These VOCs aretransported downwind to rural regions (Rice 

### et al., 1986; Rippen 

### et al., 1987; Shah and Singh, 1988; Schroederand Lane, 1988). Reverse transport also occurs; although 

### having highest concentrations in agricultural areas, chlorinated pesticides are regularly found in urban air (Abbott 

### etal., 1966; Stanley

### et al., 1971; Kaushik 

### et al., 1987; Bruckmann et al., 1988). Natural vegetation, especiallytrees. puts out substantial quantities ofVOCs. primarily monoterpenes, which mixwith anthropogenicVOCs (Roberts et al., 1985; Trainer et al., 1987; Kreuzig et al., 1988; Petersson, 1988}. Table 1 summarizes the range of concentrations ofselected organics measured in air and rain.

TABLE 1. CONCENTRATIONS OF SOME PESTICIDES, PCBS, PAHS AND OTHER VOLATILE ORGANIC COMPOUNDS IN AIR AND WATER, UNITED STATES• Compound Air

**(ngjm~** Rain {ngjL)

Hexachlorobenzene

**0.13~.29** 0.40-1.0 a.-j..,...HCH 0.30-5.4 6.4-37 DDT/DOE

**0.02~.33** 0.50-4.3 Chlordane 0.04-1.3 trace-2.3 Dieldrin

**0.02~.08** 0.8-2.0 Toxaphene 0.6-13.1 7.31-59 PCBs 0.06-9.3 0.10-200 Pthalate esters 1.0-290 >200 Benzo(a)pyrene 1.3-500 2.2-7.3 Formaldehyde 2375-12250

### b <0.01-1.1 Acetaldehyde 

### o-9900b <0.04-1.1 Benzene 1950-10700

### b e Phenol 

### 39-430b <1G-14000 Benzo(a)pyrene

**0.01~1**

•Sources: Pearson (1982), Nriagu and Simmons (1984), Giam 

### et al. {1984), Chapman 

### et al. (1986),

Atlas and Giam (1988), Shah and Singh {1988), Leuenberger

### et al. (1988), Dulnker and Bouchertall (1989), Sawicki 

### et al. (1960)

olower jupperquartiles

e no data

**availa~e** 

### 65Wet Deoositlon

The flux 

### clorganics toterrestrial ecosystems 

### in precipitation 

### is simplythevolume-weighted product 

### clthe concentration In solution and precipitation volume, summed overthe tirne 

### period of interest. 

### A. growing literature reports concentrations 

### d organic compounds In rain. Most regularly and widely detected are organic acids, especiaJiy aldehydes 

### such asformate and acetate (Chapman 

### et

## at., 1986 and references therein; Gaffney

### etal., 1987). Chlorinated pesticides, PCBs, phenols, and n-alkanes have all been reported 

### In rain (Eisenreich etal., 1981; Farmer and Wade, 1986; 

### Agarwal et 

### al., 1987; 

### Gaffney et 

### al., 1987; Jones et 

### al., 1989; Leuenberger

### at al., 1988; Atlas and Giam, 1988).

FfNI estimates 

### ofwet depositionflux for organics exist. Farmerand Wade (1986) observed 22 to 670 JJQ/rn2/dayfor C,2- C32hydrocarbon fluxes 

### at Norfolk, VA. 

### An estimatefor bulk precipitation, which incorporates some aerosols, was 40 and 20 pgfm2 /yfor PCBs and lindane, respectively, at Paris, France (Chevreuil et 

### al., 1989). Precipitation falling ontothe Great Lakes has been analyzed for PCBs and pesticidesfor some years. Deposition rates are 0.6to9.6pgfm2 /yfor chlorinated hydrocarbons, 424 pgfm2 /Yfor PAHs, and 120 pgjm2 jyfor PCBs (Nriagu and Simmons, 

### 1984).

Drv Deoosition
Dry deposition ofatmospheric substances onto natural vegetation is described bythe equation

where F 

## =flux density, C.

## = atmospheric concentration at a reference height above the vegetation, and Vd = deposition velocity. Deposition velocity has four components:

where r.

### = bulk aerodynamic resistance, rb 

### = leaf or

### sol boundary layer resistance, r.

### = stomatal resistance, and rc

## = chemical resistance.
Aerodynamic resistance represents

### theturbulent downward movement 

### of parcels

### c1 air, carrying entrained gases and particles. 

### It is affected bywind 

### speed,the surface area, and vertical distribution

### ofcanopy components (foliage, branches, etc.). Boundary layer resistances are related to wind speed and wind direction, and to collecting surface size and geometry. Stomatal resistance is

66directly proportional to

### stomatal aperture, which 

### is under physiological control by plants. Chemical resistance comes Into play whenthe concentration 

### d the compound 

### atthe absorbing surface

### is not
zero (i.e., It 

### is not quantitatively destroyed orsequestered upondeposition). Inthis case, the concentration gradient driving flux wll be

### lessthan C•.
Deposition 

### d gaseous organics occurs primarlytodrysol and vegetation surfaces and Is controlled largely by salubRity in

### the

### waxy cuticles 

### d plant surfaces and

### vapor-sol particle partitioning. Absorption 

### d gaseous organics Intowater is Important

### towet sols, on plant surfacesfollowing rain or during fog and dew events, In permanent wetlands, and 

### In riparian areas duringflooding. Deposition of organics

### In aerosol form 

### Is achieved bythe same mechanisms asforaerosols 

### In 

### general: sedimentation, diffusion, and impaction. Sedimentation is most Importantfor 

### large aerosols, diffusion for small aerosols, and Impactionfor Intermediate-sized aerosols (Garland 

### etal., 1988).
Dry deposition 

### of organics has been measured directly byaccumulation on surrogate surfaces, Including silicon oil-coated nylon screens (Sodergren, 1972); glass plates sprayed with mineral oil orwater (McClure and Lagrange, 1977; Murphy, 1984); stainless 

### steel funnels and sinks (Farmer and Wade, 1986; Chevreuil 

### et al., 1989); and pans filled with water, ethylene glycol-water, or glycerin-water (Bidleman and Christensen, 1979; Christensen et al., 1979). Observed fluxes have been In the range 10-3to 102J.Ig/m2 jdayfor PCBs and various pesticides, yielding Vdvalues of less than 0.01 to morethan 5 cmjs. Confidence in these fluxes is 

### not high becausethe efficiency collection of surrogate surfaces mayvary substantially from that 

### of natural surfaces. Bidlernan and Christensen (1979) found that Vdfor PCBs, chlordane, and DDTvaried geographically and by onetotwo orders of magnitudefrom day-to-day. In addition, aerosol and gaseous deposition cannot be distinguished, and volatilization 

### of adsorbed gases Is 

### not accounted for. Depositionvelocities measured byaccumulation have been used to infer dry deposition tothe Great Lakes from known concentrations 

### oforganics in air (Eisenreich et al., 1981).
Fogs. Clouds. and Dew


### Cioud waterand fog water contain higher concentrations 

### d organic acids

### and much higher concentrations

### d pesticides than does rain (Glotfelty

### et al., 1987; lgawa et al., 1989; Munger

### etal., 1989; Schaefer

### et al., 1989). Organic acids have also 

### been reported

### from dew 

### (Mulawa 

### et al., 1986).
Interception of

### cloud water and

### d advective (seacoast) fog water

### Is modeled as a dry deposition process, 

### with cloud and fog droplets acting like 

### large aerosols 

### (Lovett, 1984). Deposition of radiation (valley) 

### fog water

### Is simDar to 

### precipitation O.e., gravitational settling 

### d waterdroplets). Dewsform bycondensation ofwater vapor onto surfaces whosetemperature dropstothe dewpoint;



### 67deposition rates can be predicted using the Penman-Monteith equation. Organics enter dews by gaseous absorption and aerosol sedimentation. There appearto be no deposition estimates for organics in fogs, clouds, and dews.

Total Atmospheric Deoosition

Accumulation rates of persistent (slowto degrade) organics in sediments yield an estimate of net atmospheric deposition (i.e., not accounting forvolatDization). Forexample, Heit

### et al. (1981, 1988) and Gschwend and Hites (1981) measured PAHs In lacustrine and marine sediment cores in the northeastern United States. Ruxes in recent decades ranged from 36 to4,870 1Jg/m2 

### fy, with greater fluxes near urban areas. Jones et al., (1989) measured PAHs in archrved, dry soil samples collected since 1843 in rural England. Mean deposition rates (1880-1980) were 4,560 1Jg/m2 jy. Wickstrom and Tolonen (1987) found that PAH fluxes into sediments of small Finnish lakes had increased substantially since the earty nineteenth century.
Swackhamer and Armstrong (1986) estimated net atmospheric deposition of21Jg/m2 /y of PCBs in recent decades to several small seepage lakes in Wisconsin. Rapaport and Eisenreich (1988) measured PCBs, HCB, DDT, and toxaphene accumulation in peat bog sediments. Maximum deposition rates in the eastern United States occurred between 1960 and 1978, with reduced rates since 1980.

The only estimate that could be found for recent atmospheric deposition of an organic to a terrestrial ecosystem was that of Matzner (1984) for German beech and spruce forests. Assuming no root uptake or exchange between surface deposits and canopytissues, he estimated total PAH fluxes of 0.25 to 0.69 Jlgfm2 fy.

A regional application of mass balance was applied tothe Great lakes bythe International Joint Commission (summarized in Elder et al., 1988). Measurements of PCBs and pesticide concentrations in dated sediments yielded values for long-term inputs. When known contributions of tributaries, runoff, and point sources were subtracted from these values, and outflows added, the difference was ascribableto atmospheric deposition. The atmosphere accounts for 60% of PCB inputs and 78% of benzo[a]pyrene inputs to

### the Great Lakes.

68

### FLUXES OUTSIDE OF PLANTS Fates In Soil
Once deposited, the disappearance

# a organics in 

### sols usuallyfollows first-order kinetics, provided no additional input 

### occurs, 

### and plant 

### uptake 

### Is either

### constant or

### absent (Ryan et al., 1988). Factors contributing to

### thedisappearance

# a organics Include

### volatlization, photodecomposttion, adsorption to

### sol particles, 

### chemical and biological 

### (microbial) degradation, unsaturated 

### and saturated flow, and leaching to deeper 

### sol layers (Figure 1 ). 

### Consideration

# athese processes (except volatilization) 

### Is beyond the scope

# athis 

### paper. However, 

### modeling

# adisappearance rates 

### Is useful In determining 

### the likelihood

# a organics toaccum&.Ntetoconcentrations

### atwhich plant root 

### uptake will become 

### significant (Ryan et al., 1988).
Volatilization

In general, volatilization rates of organics from plant canopies Increase with 

### increasing vapor pressures and decreasing Henry's law 

### constants (H). FoliarvolatUization rates do

### notfit 

### simple firstorder kinetics because 

### ofdiurnal variability in environmental conditions 

### (solar radiation, wind speed, etc.), and plant uptake (Willis 

### etal., 1986). There is 

### no simple relationship between volatilization rates of organics from soils and eithervapor pressure or Hvalues; such factors as adsorption coefficients to soil particles and soil moisture content are also Important (Kizeret al., 1979; Mackay

### etal., 1986; Spencer et al., 1988). Measured volatilization losses of herbicides In agricultural fields show great variability; 4.5% peryearfor dieldrin, but 

### lessthan 1% peryearfor carbofuran (Caro et al., 1976); 80% peryearfor PCBs (Moza et al., 1979); 8, 24, and 34% overa six-(iay period fortoxaphene, parathion, and fenvalerate, respectively

**(W~Iis** 

### etal., 1986): less than 1% over seven daysfordiclofop (Smith et al., 1986); and 21% overfive 

### clays for 2,4-0 (Groveret al., 1985).

A substantial proportion of herbicides volatDized from soils can be redeposited on crop canopies, especially

### DDT, PCBs, and the nltrophenol dlnoseb (Parker, 1966; Prendeville, 1968; Beall and Nash, 1971; Kaufman, 1976; Moza 

### etal., 1979; Fries and Marrow, 1981; Bacci and Gaggl, 1985). Topp et al. (1986) found that the proportion ofsol-applied organic 

### chemical uptake by barleyfoliage increased as 

### thevolatilized fraction of applied chemical increased.
Wash-Off and Resuspension
Wash-off occurswhen rain physically dislodges particles orcarries away dissolved gases and particulates from plant surfaces; these are

### then deposited tothe 

### sol in throughfall (Figures 1and 2). The highest proportion of

### wash-off toamount applied is

### for pesticides with high solubDity in water, for

69those applied in particulateform, and 

### when 

### heavy or repeated rains occurshortlyafterapplication. Time-course 

### studies 

### d individual rain events reveal 

### that

### wastHlff

### Is rapid 

### atfirst, 

### then diminishes asymptoticallytoward zero. Wash-off increaseswith 

### Increasing rain amount, upto

### some saturating intensity Qsensea and 

### Jones, 1971; Steffens and Weineke, 

### 1975; 

### Cohen and Steinmetz, 

### 1986; Willis et 

### al., 1986). 

### Resuspenslon 

### Isthe raentrainment 

### r:iparticles deposited 

### on plant surfaces 

### in 

### moving air (Figure 

### 2}. Particle adhesion and windspeed are

### the primary

### factors lnlluenclng this 

### process (Nicholson, 

### 1988). 

### Soil partides may be entrained 

### In

### the atmosphere 

### (wind erosion) orejected into 

### the air by raindrop splash (Chamber1aln, 

### 1975), from

### whencethey may be redeposited 

### on plant surfaces (Pinder and McLeod, 

### 1988).

FlUXES INVOLVING PLANTS
Organics must penetrate planttissues beforethey can exert physiological effects. Thus, aerosol deposition and nonstomatal deposition 

### d gases are appropriately considered as separate processes from plant uptake. In the case 

### r:i stomatal absorption, deposition and uptake are equivalent because the sink 

### Is the mesophyll.
Uptake rates are determined by external concentration, concentration in planttissues. and resistances to uptake. For shoots, the most Important physical barrier Is the cuticle. For roots, the cell membranes ofthe endodermis are a significant barrier. Following uptake, 

### ifthe substance Is not translocated 

### or metabolized to other forms. It may accumulate in

### tissues, reducing the concentration gradient across the plant surface, and thc;s reducing flux. Translocation to other parts of

### the plant, or metabolic conversion to other compounds, will lower Internal concentratiori nearthe sites 

### r:i uptake, maintaining the concentration gradient.

Foliar Uotake ofVaoor-Phase Organics 

### Radioisotope studies 

### with carbon-14 (14

### C) labeled 

### organics have demonstrated

### that 

### In most plant species. uptake 

### r:i PCBs 

### Is primarily by leaf

### vaporabsorption, even when

### the PCBs areapplied to the 

### sol (Nash and Beall, 

### 1970; Iwata and Gunther, 

### 1976; Weber

### and Mrozek, 

### 1979;

### Bacci and Gaggi, 

### 1985). Nash and 

### Beall (1970) and Beall 

### and Nash (1971) found the 

### same to betrue

### of soybean 

### plants 

### exposed to sol-applied

### DDT, but 

### sol volatKization

## was less Important

### for dieldrin, aldrin. and heptachlor. PCBs accumulate 

### in both herbaceous and woodyspecies 

### in proportionto PCB concentration in the surrounding atmosphere (Buckley, 1982). Soybeans absorbed 1

## "C70anthracene

### vaporsfrom air (Edwards et al., 1982). 

### AccumUation c:i PCSs, DOT, penta-chlorophenol (PCP), nitrophenols, dioxins, furans, 

### and DGohexachlorocydohexane (CG-HCH) also occurs

### In conifer foliage (Eriksson 

### et al., 1989; Hinkel et

### al., 1989, Reischl 

### at al., 1989a).

Gaseous hydrocarbons are raadYy 

### absorbed by

### plantfoliage. 

### When tomato. barley. and carrot plantswere 

### exposed to hydrocarbonvapors (2 x 10-4M).

### foliar damage symptomsappeared rapidly (Currier, 1951; Currier

### and Peoples. 1954). Frank

### and Frank (1989} 

### exposed 

### Norwayspruce saplingstotetrachloroethane 

### in 

### glass chambers. 

### The 

### concentration c:i

### tetrachloroethane In the needles (Cn) Increased linearty with Increasing 

### concentration In

### thechamber air. At Cn 

### < 5



### pgfcm~ 

### the partitioning between air and needleswas greater

### thanwhen 

### en> 10



### pgfcm~ 

### suggesting surface adsorption, folltwied by cuticularabsorptionwhen adsorption capacity

### was saturated.

Wolverton et 

### al. (1984) reported that house plants absorbed formaldehyde from

### theair. However. additional experiments byGodish and Guindon (1989) established that the absorption

## was by potting soil rather than the plants. Bioconcentration 

### of vapor -phase organics in leaves

### Is closely correlated with their octanol-water partition coeffteients [(K_ (Figure 3); Travisand Hattemer-Frey, 1988; Reisch! et 

### al., 1989b].

Foliar Uptake of Uauid-Pbase Organics

Penetration ofthe cuticle by herbicides applied in solutions is positively related totheir K_ values (Shafer and Schonherr, 1985) and Is usually linearty related to herbicide concentration (Bukovac, 1976). Uptake 

### is generally greaterto adaxial than to abaxial leaf surfaces, apparently because 

### of the higher density ofstomata and greater pubescencethat occur on

### adaxial surfaces (Sargent and Blackman, 1962; Bukovac, 1976). Trichome bases and guard cells are preferred locations of uptake. Mass movementthrough stomata occurs If

### the organic, or 

### its solvent, are lipophilic and have low surface tension (Baker, 1970; Bukovac, 1976). Most studies 

### offoliar liquid uptake by herbicides, using 1

### "C labeling, havefound substantial uptake (Bukovac, 1976; Steffens and Wieneke, 1975; van Auken and Hulse, 1979), 

### but

**2.~ichlorophenol** and dioxin do

### not appearto penetratethe cuticle Osensee and Jones, 1971).

When Currier (1951) and Currier

### and Peoples (1954) 

### exposed plantsto pure hydrocarbon liquids, development 

### c:ifoliar damagewas 

### rapid, Implying

### fast uptake across

### the cuticle. Ina literature 

### revie'Non hydrocarbon

### ol elfects on 

### plants. Baker (1970) concluded thatthose

### ols containing mostly small-molerue. IOIN-volatllty hydrocarbonswith low

### viscosityare most phytotoxic; 

### the hydrocarbon constituents readlydiffuse across cuticles

### and cell membranes, evaporative losses
are lowwhen applied to sols orfoliage, and 

### penetration through stomata occurs.



### 71

### 6~----------------------------------------------~

5



### 4



## , , , 

## , , a-HCH

### .'J" 

## ,4

, " lindane

4 

### , , 

### , , 

### , , , , 

### , , 

## , ,

5 LOG 

## Kow ,' 

## , , 

## , , 

## , p,p'-DDT , , ' 

# . ,'**p,p'-DD~** - , '


### , , ePCBs 

### , 

### , , , ,

6 7

FIGURE 3. The relationship between bloconcentration 

### of organics in plant tissues**(B~;** ratio of concentration In plant to concentration In air) and the octanol-water partition coefficient (K_) (after Travis and Hattemer-Frey, 1988).



### 72Foliar Uotake of Solid-Phase Organics
Organics are frequently

### adsorbedto

### the surfaces 

### d atmospheric aerosols, 

### but no

### studies 

### of particle-associated organic uptake by plants have 

### been conducted. However, cuticularabsorption

### of lipophilic organics 

### Is probably 

### much faster from

### the

### vapor phase

### than from

### the

### solid phase (Reisch! et 

### al., 1989b}.

Root Uptake

Manr different herbicides are

### absorbed by

### the roots

### d crop 

### plants (Uchtenstein

### and Schultz. 1965; Lichtenstein 

### et al., 1967; Shone and 

### Wood 1974; Bukovac 1976; Hlton 3l

### al.• 1976; Briggs et 

### al., 1982; WICkliff et 

### al., 1984; McFarlane and

### Wickliff, 1985; 

### Scheunert

### at al., 1986; Topp et 

### al., 1986; McFarlane et al. 1987a,b). A linear relationship 

### Is often observed between 

### soil or growth solution concentrations and rates of uptake, 

### at least when concentrations are low. At higherconcentrations, uptake may

### be saturated or even reduced (Aetcheret al.,**~990),** perhaps duetodirecttoxicitytothe roots. Ifthe original herbicide Is

### not very soluble, root uptake rates may instead be related to concentrations ofsoluble 

### sol metabolites (Scheunert

### et al., 1986).

Root uptake has been documented forthe insecticides dieldrin, endrin, aldrin, and lindane, but does not occurfor DDT and heptachlor**(Ha~** and Sans, 1967; Lichtenstein et

### al., 1967; Nash et

### al., 1970). Root uptake has also been observed fordioxins, benzene and substituted benzenes, phenol and substituted phenols, ethanol, naphthol, acetate, tiaryl phosphate esters, pthalate esters, organoborates, and trinitrotoluene (Harley and Beevers, 1963; 

### Isensee and Jones, 1971; Kaufman, 1976; Suzuki et al., 1977; Moza et 

### al., 1979; Mrozek and Leidy, 1981; Shea et

### al., 1982; Edwards, 1983, 1986; Casterline et al., 1985; McFarlane and Wackliff, 1985; Scheunert etai., 1985, 1986, 1989; Facchetti et al., 1986; Palazzo and Leggett, 1986; Sacchi et al., 1956; Topp et 

### al., 1986; McFarlane et 

### al., 1987a,b; Adriano et 

### al., 1988; Aranda et al., 1989; 

### Krstich and Schwarz, 1989; Retcher et 

### al., 1990; McFarlane et

### al., 1990; O'Connor et 

### al., 1990). Depending on

### the species, plant roots mayor may not absorb PCBs and PAHs {Edwards 1983, 1986; O'Connor etal., 1990).
During root uptake, organics move bydiffusion 

### In

### the apoplasticwater

### d the cortex; then, at 

### the Casparian strip, cross

### the cell membranes

### c:Athe endodennlsto reach

### thexylem. Shone and 

### Wood (1974), Briggs et 

### al. {1982, 1983), Topp et al. (1986), and McCradyet

### al. {1987) found a positive,**l~lnear** relationship between

### the root

### concentration factor 

### (RCF; 

### ratio 

### of roottissue concentration to 

### external solution

### concentration) and K_for various organics. HO'Never, 

### In a comparison of nitrobenzene absorption by eight plant species, RCF varied considerably around the



### 73predicted value from Briggs et 

### al. (1962), emphasizingthe importance

### d species-specific characteristics (McFar1ane et al., 1990).

Bark Uptake

Penetration 

### d the bark

### d woody plants by herbicides

### has been reported (Bukavac, 1976). Meredith and Hites (1987) 

### found a 

### variety 

### d PCB 

### congeners lri the bark of blackwalnut andtUiiJr poplartrees growing neara PCB-contaminated 

### landfill. 

### Very kM' PCB

### concentrations In 

### thewood, much higher PCB concentrations in innerthan in outer

## bark. and a positive correlation between congener K_and accumt.Ation 

### in outer 

### bark suggested that uptake occurredfrom

### the atmosphere into the suberin 

### d cork cells.

Translocation

When 14

### C-labeled herbicides are taken up by roots, 

### most move upward in

### thetranspiration stream, but some remain inthe cortex, apparently unableto cross the endodermis (Hay, 1976; Hilton et al., 1976). The proportiontranslocated varies according to length 

### clexposure, plant species, and 

### type of herbicide (McFartane et al., 1987b). What 

### is translocated may

### befound fairty uniformly in all 

### the leaves or may 

### be concentrated in young leaves and growingtips (Hay, 1976). 

### Dry soils reduce rates oftranslocation, presumably dueto lesser transpiration and a lowercarbohydrate supplyfor phloem transport.

Translocation of root-absorbed, non-herbicide organics has been demonstrated for aldrin, lindane, bromacn, triaryl phosphate esters, phenol and chlorophenols, dioxins, pthalate esters, PCBs, trinitiotoluene, and nitrobenzenes (Uchtenstein et al., 1967; Isensee and Jones, 1971; Mrozek and Leigy, 1981; Shea et al., 1982; Castertine et al., 1985; Edwards, 1986; Palazzo and leggett, 1986; Sacchi et al., 1986; McFartane et al., 1987a,b, 1990; 

### Aranda et al., 1989; Aetcher et al., 1990). Rootand leaf-absorbed hydrocarbon oHs are transported acropetallyand baslpetally, respectively (Buckley, 1982). However, there 

### is little translocation 

### d root-absorbed PCBs, PAHs, and substituted phenols (Hilton

### et

### aJ., 1976; Kaufman, 1976; 

### DOrr, 1970; Buckley, 1962; 

### Scheunert at aJ., 1989), nordo root- or 

### leaf-absorbed dioxins and furans appearto

### betranslocated 

### (Reischl et al., 1989b).

There 

### Is considerable evidencefora positive relationship betweentranspiration rate and root uptake (see Figure 4) (Bukavac, 1976; van

## Oorschot. 1976; Mcfarlane

### atal., 1987b). However, Shone and Wood (1976) discovered that 

### neitherexternal concemation nor

### transpiration rate had much effect on uptake and

### translocation 

### d triazine herbicides 

### byradish.



### 74

# - Cl :1 

# -**1.6~------------------------------------------------~~**

1.2



### 0.4 ExposureTime:

• 3d8)'S 

## 0 Sdays A 

### 7days 

## 6 10days

atrazineinwheat

## o.ok:~--------~------------_.--------------------------~ 0.0 0.4 0.8 1.2 1.6 TranspirationxSolutionConcentration(pg)

FIGURE 4. The relationship between 

### total uptake ofatrazine from solution 

### by

### wheat and 

### the expected uptake 

### by mass flowthrough 

### the xytem (after Walker, 1972).

75Briggs et al. (1983) observed a positive, log-linear relationship 

### between stem concentration factor (SCF; calculated In 

### same way 

### as RCF) 

### and herbicide 

### K_. It required 24to

### 48 h for

### SCFto stabilize, with longerequllbration

### times for higher

### K_. They postuated

### that stable

### SCF represented abalance 

### between upward transport

### eX root-absorbed compounds

### andtheirabsorption ordegradation by stem tissues.

The 

### herbicide transpiration

### stream concentration factor 

### (J'SCF; 

### ratio eX cor.ce1

### lbation in transpiration stream to concentration 

### In external solution) 

### In barley

### plants

## was usually

### lessthan unity, implying passive uptake

### eX most 

### herbicides, but

### greater

### than unity

### for 2,4-0. Implying active uptake (Shone etal., 1973; 

### Shone and Wood. 1974). The 

### mltrobenzene

### TSCF

## was consistently

### less than one 

### In eight plant species (McFartane

### et

### al.• 1990). 

### TheTSCF

## was nat related 

### In any

### obvious wayto RCF. However, 

### Shone et

### al. (1974) demonstrated

### thatthe

### TSCF was correlated

### w!th the most readily diffusible herbicidefraction In barley roots duted with waterfollowing

### a period

### eX

### root uptake. This fraction consisted ofthe 

### most lipophilic (high 

### K_) herbicides. Briggs et al. (1982} observed a bell-shaped relationship between TSCF and K_ln barley (Figure 

### 5). They hypothesized that for 

### K_ < 1.8, transport is limited bydiffusion across

### the endodermal membrane; whereas, for 

### K_ > 1.8, transport 

### is limited bythe rate 

### eXtransport

### from the roots tothetops. McCrady et

### al. (1987) demonstrated that 

### sorption to

### thexylem

### tissue was

### the main limitation on transport rates oforganics through excised soybean stems. McFartane 

### etal. (1987b) found differential root uptake and translocation tothe 

### shoot 

### eX soybean by bromacl, nitrobenzene, and phenol, although thethree chemicals have simUar 

### K_values. Given the scatter in Briggs et al. {1982) relationship, this result is not surprising. 

### Boersma et

### al. (1968) have developed a model 

### of organic compound transport In the xylem and phloem. This model 

### is most sensitiveto 

### K_. rates of detoxification, membrane permeabUity, and the volume ofxylem and phloem in various organs. Generally, the bulk 

### offoliar-applied organics 

### Is nottranslocated; that portion that 

### is partitioned tothe stem, little

### goes to the roots (Hay, 1976; 

### Shone and Wood, 1976; Weber and Mrozek, 1979). Foliar-applied ureas, 

### triazlnes, DNOC, PCP, and hexachlorophene are nottranslocated (Fogg, 1948; 

### Hay. 1976; Kaufman, 1976; 

### van Auken 

### and Huse. 1979).
Detoxification


### Plants detoxify 

### herbicides prlmarly by metabolic degradation and to a 

### lesser extent by adsorptionto 

### biomoi8CUes. Adsorption to lecithin and 

### cell membranes has

### been demonstrated for 2,4-0 and 2,4,5-T (Wain 

### and 

### Smith, 1976). 

### The metabolic

### fates c:lmanydifferent 

### herbicides have been aucidated by 14C labeling studies (Naylor. 1976). In

### most

### cases, metabolism converts

### the

76

### 1.0 

# • barley 

### 0.8 

## - 

# • 0.6

**~** 

# • •

_...

# -.---

**~** '

# .... u \1'1 

# ,._,.. 

# •
...

**~** 

# • ...

.... 

### 0.4 

### , , 

# ' , 

## ' , 

# • ' , 

# • , ' , ' 

## , ' 0.2 

# . , 

# • \ 

## , 

# e,' \



### , , 

# • \ \ 

# • ,

# . \ 

### 0.0

# _, 0 1 

### 2 

### 3 4 

### 5 LOG

## Kow

FIGURE 5. The relationship between transpiration stream concentration factor (TSCF; ratio 

### of concentration in transpiration stream:concentration In nutrient solution) 

### c:lvarious organics and octanol-water partition coefficients (K_) In barley (after Briggs et al., 1982).



### 77phytotoxic herbicideto nonphytotoxic or less phytotoxicforms; however, 

### the reverse 

### is sometimes true (e.g., amitrole, bipyridyliums, 

### 2,4-D precursors, DNOC esters) (Wain and Smith, 1976; Menn and 

### Still, 19n). Generally, detoxifteation proceeds 

### in two steps: (1) an oxidizing, reducing, or hydrolyzing reaction that modifies the organictoxin by adding reactive groups; and 

### (2) 

## a subsequent conjugation reaction that further reduces toxicity

### and yields a metabolite 

### In 

### a form suitablefor storage 

### or transport (Kaufman, 1976; Menn 

### and Stll, 1977).

The 

### metabolic fates 

### of

### most nonherbicide organics 

### in plantsare

### not well understood. Degradation 

### of 

### PAHs, pthalate esters, 4-nitrophenol dichlorobiphenyts, nitrobenzenes and trinitrotoluene have been reported 

### (000. 1970; Moza

### et al., 1979; Edwards, 1986; Palazzo and Leggett. 1986; McFar1ane et

### al., 1987a, 1990; Aetcher et

## at., 1990; Preiss

### et al., 1989; Schmitzer et al., 

### 1988). butthe phytotoxicity

### ofthe metabolites 

### is unknown.

One major mechanism 

### of plant detoxification 

### cl organics 

### Is conjugation to glutathione. For example, com, sorghum, and sugarcane, which possess this metabolic capability, resist atrazine; whereas broadleaf weeds and grasses, which do not have this capability, are susceptibleto atrazine. Schroder and Rennenberg (1989) reported glutathione conjugation 

### of pentachloronitrobenzene (often sprayed on cropsto protect them from pathogens). but not 

### ofatrazine, by Norway spruce.

Plant 

### Efflux
Efflux 

### of organics from plants occurs in three ways: (1) foliar 

### efflux or •leaching: 

### (2) passive loss bytranspiration, and 

### {3) root exudation (Rovira, 1969; Tukey, 1970). Radiocarbon studies have shown that root exudation 

### of herbicides is an energy-requiring process, occurs in the zone

### of active root elongation, and involves readily translocatable and little-metabolized herbicides (Bukovac, 1976). The extent towhich organics taken up by plants may be subsequently

### lost byfoliar 

### efflux apparently has not been studied.
Siddaramappa and Watanabe (1979) exposed 

### rice plants to 14C-carbofuran in nutrient solutions 

### sealed

### at the root collarto prevent volatUized carbofuran from reaching the leaves. Transpired carbofuran wastrapped 

### in ethylene 

### rjycol in 

### shoot chambers. Over

## a 1(kiay

### period, 9 to 17% ofthe absorbed radioactivitywas 

### lost

### via transpiration, apparently carbofuran

### was carried passively along inxylem water. Highertranspiration rates 

### resulted in more carbofuran recovered from the air. 

### These authors alsofound significant radioactivity 

### In guttationwater. McFarlane

### etal. (1990) found that 10-40% of 

### not -absorbed

**~**..C-nitrobenzene volatilized 

### from leaves 

### d crops and woody plants.



## 78KNOWN EFFECTS ON PLANTS Visual lniurv and Growth



### As with plant uptake, there 

### is a close association between K_values 

### oforganics and their inhibitory effects on plant germination and growth. A 

### good model that

### fits a wide range 

### of plant data 

### is a nonlinear equationwhere toxicity increases linearty uptoa 

### critical valued 

### K_. then falls off at higher K_(Hansch

### etal., 1989).

Herbicides The mechanisms bywhich herbicides Influence growth Include Inhibition

### d mitosis, inhibition
or stimulation 

### d tissue enlargement and 

### elongation, and alteration

### d patterns 

### d tissue differentiation (Cartwright, 1976). Herbicides mayalso alter dry mass distribution among plant organs, prevent poliination, and cause abscission 

### ofleaves and other plant parts (Addicott, 1976; Ratsch et al., 1986); and, in the case 

### of

**auxin~ike** herbicides such as 2,4-0, abnormal growth 

### ofvarious organs (van Andel et al., 1976). Effects may be manifested at all stages 

### of growth from germination to reproduction. For example, Sund and Nomura {1963) observed that some herbicideswere

### most effective in inhibiting germination, others at Inhibiting seedling growth, and still others at inhibiting growth 

### of juvenile plants. Several herbicides, Including dinoseb, PCP, 2,4-0 and 2,4,5-T were inhibitory attwo
or more 

### ofthese life stages.
Substituted phenolsvary widely In their effects on germination and seedling growth (Sund and Nomura, 1963; Amer and Ali, 1968; Shea et al., 1983). Root growth 

### Is stimulated by2,4-dinitrophenol (DNP) at low concentrations and is Inhibited at high concentrations, probably because it is a respiratory uncoupler (Shea et 

### al., 1983). Chlorosis, wilting, and necrosis of peas Is caused by 2-nitrophenol and 2,4-dichlorophenol (Amer and Ali, 1968).

Van 

### Haut and Prinz {1979) studied the effects ofa number of organic vapors onthe growth of several crop species. Over a wide ranged concentrations (0.1-7.0 mg m

### -s). relative growth reductions were positive

**log~inear**for all chemicals and 

### species studied. Growth reductions relative tothose caused by sulfur dioxide

### at equivalent concentrationsvaried between plant species and were usually higher

### at lower

### concentrations. 

### The 

### most phytotoxic substancewas ethylene (upto eight timesthe growth reduction of sulfurdioxide), followed byformaldehyde and acetic acid. Dimethylformamide and methanol were

### less phytotoxicthan 

### StJfur dioxide. Dichloromethane, toluene, trichloroethylene, acetone, andxylene caused little or no growth reduction at concentrations upto 

### 60-160 

### mg/rn3•



### 79Surfactants are often 

### used to improve 

### "wettability'" 

### c:ifoliar-applied herbicides. These substances may In themselves Increase, reduce, or have noeffect on

### the growth of crops (Uchtenstein 

### et al., 1967; Singh and Orsenlgo, 1984).

Other Organics Toxicity 

### c:ipure hydrocarbon

### sprays applied to 

### plants 

### Increases In 

### the order: straight-chain paraffins 

### < napthenes and alkenes 

### < aromatics 

### (Crafts

### and Reiber, 1948). When bartey, tomatoes, and carrots were 

### exposedto hydrocarbon

### vapors, toxicity increased 

### In the order: benzene 

### < toluene



### < xylene 

### < trimethylbenzene (Currier, 1951}. 

### The symptoms started 

### with increased foliage odor, followed bythe appearance 

### c:idark areas onthe

### foliage, 

### v.-iting, 

### and, 

### at higher concentrations, death. Shoot

**d~.l** mass gain was positively correlated 

### with vapor concentration forsublethal doses. When these same compoundswere sprayed onfoliage as pure liquids, the same order

### c:itoxicity was observed, butthe differences among hydrocarbonswere greater, apparently because 

### of differences in volatilization (vapor pressure decreasing in reverse ordertotoxicity). Currier and Peoples (1954) repeated these experiments, finding that toxicity Increased in the order: hexene 

### < hexane 

### < cyclohexane < cyclohexene < benzene.

Crude oils, their refined products, and 

### coal liquid cause visual Injuryand reduce growth of a variety ofweed and crop species (Baker, 1970; Blankenship and I.Jlrson, 1978; Wamer et al., 1984). Toxicity is duetothe mixture 

### of hydrocarbons In these liquids, including alkanes, alkenes, napthenes, naphthalenes, phenols, and aromatics. Many hydrocarbons are 

### known to betoxic inthe presence of ultraviolet radiation (Larson and Berenbaum, 1988). For example, the PAH fluoranthene causes foliar injury under UV light (Zweig and Nachtigal!, 1975). Creosote, a widely used wood preservative, contains a variety 

### of PAHs and other aromatics. Concentrations of 18to 34 mgjL reduced root growth of onion by50% (Sundstrom

### et al., 1986).

Aroclor 1254, a mixture of PCBs, Inhibited height growth and fresh mass Increase of both soybean shoots and roots; at higher concentrations, newlyformed leaves showed abnormal curting (Weber and Mrozek, 1979). Pthalate esters caused 

### reduced growth and chlorosis 

### of ll8"N leaves and growingtips 

### oftobacco and com 

### (Buta, 1975; Shea et

## at., 1982). Tributyl phosphate reduced root growth 

### c:irice, radish, and soybean at concentrations

### of 10to 100

**~Jg/g** 

### sol (Muir, 1984). Trinitrotoluene 

### (TNT) lowered root and 

### shoot growth

# a nutsedge (Palazzo and Leggett, 1986). Sodiumtetraphenytborate (NaTPB) reduced growth 

### c:iloblolly pine 

### seedlings because

### of Increased plant boron uptaketo

### toxic levels (Kaplan 

### etal., 1988). NaTPB's majordegradation product, diphenytborlc acid (DPBA), did

### not affect growth. However, both NaTPB and DPBA, aswell as biphenyt, another breakdown product, 

### reduced growth 

### c:isorghum, with NaTPB having

### the greater Influence (Adriano et al.. 1988).



### 80Many substituted phenols have auxin-like 

### activity. 

### Harper and Wain {1969) found that the greatest growth promotion in standard auxin activity

### testswas 

### produced by phenols with substitution at both ortho-positions. Uke phenols, PAHs can stimulate plant growth (Gritand Nowak, 

### 1966). Several alcohols promoted growth

### c:X

### excised wheat roots 

### In the light, whereas 

### others had 

### no effect (Gudjonsdottir and Burstrom, 

### 1962). 

### Hexadecanol and

### docosanol decreased growth

### c:Xtobacco {Bourget and Parups, 

### 1963). Organic acids

### and aromatic 

### alcohols. aldehydes, and carboxylic acids inhibited 

### lettuce germination (Mayer

### and Evenari, 1953; Reynolds, 1978). The Insecticides parathion, diazinon, and lindane significantly reduced root growth, 

### but 

### not shoot growth, 

### d peas; whereas, simazine reduced both 

### root

### and shoot growth (Lichtenstein

### etal., 1967). Vapor-phase aldehydes at concentrations > 

### 0.2 ppm caused foliar Injuryto petunias (Brennan 

### etal., 1964).

Gas Exchange and Water Relations

Herbicides 

### For most herbicides studied to date, stimulation, Inhibition, or

### no effect on dark respiration have been reported (van Oorschot, 

### 1976). In 

### some cases, lower concentrations stimulate; whereas, higher concentrations Inhibit, a typical response for oxidative uncouplers such as DNP 

### (Shea et al., 

### 1983). Respiration mayalso be affected dtfferential1y by

### the same herbicide in different plant organs.

Inhibition of net photosynthesis has been observed in a widevariety of herbicides when plants
are exposed to herbicides In sons or nutrient solutions, orapplied tofoliage (van Oorschot, 

### 1976). With the exception ofacylamides, virtually all herbicidestested to date inhibit net photosynthesis and, when a range of concentrations 

### Is studied, Inhibition Increases with increasing concentration. Unlike respiration, stimulation of net photosynthesis has

### not been observed (van Oorshot, 

### 1976).

All herbicides that reduce net photosynthesis reduce transpiration as welt, such as ONP (Barber and Koontz, 

### 1963; Pemadesa and Korelege; 

### 1977). This phenomenon raises the question as to whether or

### not photosynthetic inhibition is primarily

### dueto stomatal closure, orto nonstomatal (biochemical) 

### effects. Nonstomatal inhibition can be represented 

### as a •mesophyll resistance• (r

## .J In series with rband r,. lmbamba and 

### Moss {1971} 

### found that r"'

### for C02 

### in com 

### exposed toatrazine increased without an accompanying change in

## r,. Most

## evidence for

### the relative roles

### d 

## r,vs. r"'

### Is indirect. however. When photosynthesis

### and transpirationwere measured simultaneouslyfollowing exposure to ureas, 

### triazines, diazines. bipyrldyliums, 

### and simeton, 

### the relative reduction 

### in photosynthesis was greaterthan

### that 

### c:Xtranspiration, and 

### commenced sooner (van 

### Oorshcot, 1976). This suggested direct herbicidal action

### atthe sites 

### cf photosynthesis. However, for PMA. DSA, ioxynll, propanll, nitrofen. and fiuorodifen, 

### photosynthesis and transpiration 

### were inhibited to a similar extent and atthe sametime, implying that stomatal closure restricted uptake of C02• Similar



### 81**~**



# ~'---­

**·~._..--** variations 

### in 

### the relative reduction 

### d



## transpirat:-:-'7"-:~ion-vs._p_f:a·w~,,l\1~ were observed 

### for nitrobenzene
.Tt.:.t.'S.i

...

**~&. ~~"'~j(~lS..•••e•**  .. (McFar1ane 

### et al., 1990). Herbicides also disrupt

### the water economy 

### d plantS 

### IJy'tWootb'tls!.'l¥OC-t

. water uptake, as reported 

### for phenoxy herbicides, uraas, 

### triazines, propanl, and dinoseb (van 

### Oorschot, 1976).

Herbicides that inhibit

### the light reactions

### d photosynthesis often Inhibit photorespiration as well. This 

### has been demonstrated by simiar

### reductions in

### net photosynthesis of

### wheat and com in airwith 

### normal and 

### low 0 2concentrations following exposuretodluron (Downton andTregunna, 1968), and by

### the absence ofthe postllumlnatlon

### C02

### burst In barley exposed toatrazine (lmbamba and Moss, 

### 1971). However, when com

## was exposed to

### atrazine, C02evolution 

### in the lightwas greaterthan in darkness, suggesting little or no

### suppression of photorespiration (van Oorschot, 

### 1976).
Other Organics Organic chemicals otherthan herbicides have been 

### shown to Influence plant growth and development. Wood et 

### al. (1985) and Wood and Payne {1986) found that pecan leaves sprayed with the fungicides propiconazole, benomyt, triphenyltin hydrcxide, and docline, orwith pyrethroid, carbamate, and organophosphate insecticides showed inhibition of net photosynthesis of upto 20% within one dayfollowing application, with full recovery usually occurring within several days. Hydrocarbon oils universally reduce transpiration and net photosynthesis ofcrops (Baker, 

### 1970). Recovery of both processes 

### Is correlated with the dissipation offoliar-applied oils, and raising the CO2 concentration 

### ofthe air reduces inhibition, suggesting that blockage of stomata 

### Is 

### th.e cause 

### of inhibition. However, due to the rapidity with which hydrocarbons penetrate leaftissues, nonstomatal effects are likely as well. Hydrocarbon oUs either increase or decrease respiration, withthe effect differing among ons and between plant species (Baker, 

### 1970). Nitrobenzene at 8 g/L in growth solution had varying effects on gas exchange of several species; ranging from no effects on soybean to complete photosynthetic repression of green ash (McFarlane et al., 1990). Even at 100 g/L. nitrobenzene did not affect soybean gas exchange (Aetcher et

### al., 1990).

One hypothesisto account for European forest-tree decline or "Waldsterben· 

### is phytotoxicity ofanthropogenic 

### and biogenic hydrocarbons. When

### young Norway

### spruce were exposed to ,.pinene vapors, photosynthesis was Inhibited and chlorophyll degraded (Grosset al., 1988; Wagner et

### al., 1989). ,.pinene inhibits

### the HUI reaction (Pauly, 

### 1981), resLJtlng In uncoupling ofoxidative phosphorylation (Wagner 

### etal., 1989). Frankand Frank (1985) were ableto reproduce

### the decline symptom of needle yellowing In Norway

### spruce by

### exposing branchestovapors oftwo anthropogenic VOCs, 

### tri- and tetrachloroethene, in

### the

### field. They later

### showed (1986, 1989) 

### that

### these compounds were absorbed by

### spruce needles and, 

### in

### the presence ofsunlight, 

### the compounds caused photodegradation of photosynthetic pigments. Rippen et

### al. {1987) have speculated that nitrophenols injure forests. 

### 82Ultrastructure and Membrane Function

Because 

### most organics are llpophUic, 

### It 

### Is 

### not surprising thattheyoften disrupt cell membranes. 

### At IOYI concentrations, dissolution

### d organic moi8CUes in membranesforces apart the 

### fatty acid chains

### d the phospholipids, Increasing membrane 

### permeability. At higher concentrations, the bUayer configuration maydisintegrate completely. 

### Some organics disrupt cell membranes indirectlythrough theformation 

### d free radicals, Inhibition 

### d lipid synthesis, or changes In 

### the types of lipids synthesized. The disruption 

### d membranes probably accountsfor many 

### d the lJtrastructural changes attributed to organics.

Herbicides Contactfoliar damage 

### rbumlng• or

### "wetness1 by2,4-0, endothal, and several other herbicides is believed to result from physical disruption of cell membranes (Morrod, 1976). Paraquat disrupts membranes because 

### Its metabolism produces hydrogen peroxide (Morrod, 1976). Two consequences of membrane damage are leakage 

### d cell contents and altered rates ofactive uptake. For example, DNP increases plant cell permeability towater, whereas stomatal closure caused by atrazine, 2,4-D, and DNP may be caused by leakage of K

.. from guard cells (Morrod, 1976; Shea et al., 1983). Ultrastructural changes induced bX herbicides in leaves Include swelling ofthylakoids and chloroplasts, destruction of phloem and vascular cambium, abnormal differentiation ofxylem, bark, and root cells, and mitotic abnormalities (Amer and Ali, 1969; Unck, 1976; Moreland and Hilton, 1976}.

Other organics Despite rather low K_values, 

### bulky hydrocarbons are effective at disrupting membranes. For example, heptene-2, with a bent configuration, causes discoloration and death of cotton hypocotyls, while straight-chain heptane shows no phytotoxicity (MomJd, 1976). 

### It has also been shown

### that ,.pinene alters the relative proportions of lipids and causes disappearance of microsomes in Norway spruce needles (Frosch et al., 1989; KJingler and Wagner, 1989}.

Translocation

Root 

### ion uptake 

### Is Inhibited by many organics. For example, nltrophenols, 2,4-0, simazine, and propanA inhibit phosphate uptake, DNP inhibits 

### Ca.2-+ uptake, the organophosphorus Insecticide Systox inhibits

# a·uptake, and phenolic acids inhibit phosphate and K+ uptake (Barber and 

### Koontz, 1963; Glass, 1973, 1974; Oertli and Ahmadi, 1975; Kaufman, 1976; Morrod, 1976). 

### As uptake ofthese ions is energy-requiring, 

### the mechanism

### d reduced uptake may

### be inhibition of respiration or uncoupling 

### of oxidative phosphorylation.



### 83Herbicides alterthe qualitative and quantitative nature 

### d solute transport in 

### plants. 

### The major effects are physical obstruction 

### of

### the phloem caused by unorganized 

### cell dMsion, blockage 

### by callose formation, localized xylernjphloem

### tissue injury ordeath, stimLAtion or inhibition 

### of metabolic sinks, and decreased transpiration (Ashton and Bayer, 1976). 

### The only reference found for a nonherbicide organicwas Wedding and 

### Riehl {1958), 

### who reported that petroleum 

### ol inhibited phosphate transportfrom roots to leaves 

### In 

### lemon seedlings.

Metabolism

Herbicides Herbicides have various modes

### ci action. Many Interfere with mitochondrial metabolism. Chloro- 

### and nitro-phenols, benzlmidazoles, nitriles, 

### and phenoxy acids are uncouplers of oxidative phosphorylation O.e., the synthesis 

### ofATP is stopped

## even though respiration continues) (Beevers, 1953; Kaufman, 1976; Kirkwood, 1976; 

### Shea et al., 1983). Substituted phenolsvarywidely in their uncoupling ability (Gaur and Beevers, 1959). Other herbicides, Including amides, benzoic acids, carbamates, dinitroanilines, halogenated aliphatics, thiocarbamates, triazines. triazoles, and ureas, reduce oxidative phosphorylation by either Inhibitingthetransfer 

### of energyto intermediates In the formation 

### ofATP, or inhibiting the flow of electrons along the electron-transport chain (Kirkwood, 1976). Glycolysis is Inhibited by halogenated aliphatics and 

### phenoxy acids; the latter also Inhibit the pentose-phosphate pathway (Kirkwood, 1976).
Many herbicides negatively affect photosynthesis. Inhibition 

### of electron transport in Photosystems 

### Iand 

### II occurs by removal or Inactivation 

### of intermediate electron transport carriers, or bythe herbicide acting as an electron acceptor in competition with 

### normal acceptors. This Inhibition is light-dependent. Uncouplers dissociate electron transport from ATP synthesis (photophosphorylation). Some herbicides are both inhibitors and uncouplers. For a comprehensive review, 

## see Moreland and Hilton (1976).

Herbicide effects 

### on Intermediate 

### metabolism are numerous. Many inhibit rates 

### of synthesis
or degradation 

### of carbohydrates, lipids, 

### proteins, and 

### nucleic acids, oralterthetypes

### ofthese compounds

### fOI'TTlGd 

### (Cherry, 1976; Kirkwood, 1976; 

### Morrod, 1976). 

### However, 2,4-D and 

### 2,4,5-T stimulate lipid synthesis 

### (Morrod, 1976). 

### Some herbicides inhibit nitrite reduction, causing nitriteto accumulate In plant tissues (Klepper, 1979).

Other Organics Fungicides (e.g., captan) inhibit respiration and photosynthesis

### atthe cellular level !n a similar
manner to herbicides (Budimir

### et al., 1976). Evidence exists for inhibition

### of gylcolysls, aerobic



### 84respiration, and uncoupling ofoxidative 

### phosphorylation by hydrocarbon ols (Baker, 

### 1970). Ravanel et al. 

### (1989) reported the uncoupling ability 

### ofchlorophenol in maple cell suspensions.

Plant Resistance

Plant 

### species differ 

### in their 

### resistance to herbicide effects, 

### and speciessensitivity rankings differ among herbicides. 

### Otherfactors 

### Influencing sensitivity are

### genotype, growth stage, 

### nutritional status, 

### physical damage, cuticUar 

### permeablity, temperature, water

### stress. light Intensity, 

### leafarea, leaf morphology, transpiration rate, and rooting depth 

### (Aberg 

### and Stecko, 

### 1976; Muzik, 

### 1976). 

### It Is well established thatthe primary causes

### of "herbicide 

### selectMt( (the 

### pesticide science term for plant sensitivity) are due primarilytothree

### factors: (1) different rates 

### d uptake bythe 

### roots 

### and/or shoots; 

### (2) different rates oftranslocation and differences 

### In the organs and

### tissues to

### which translocation occurs; and 

### (3) different capabilities for, 

### or rates 

### of, metabolic detoxification (Sargent, 

### 1976; Wain and Smith, 

### 1976). 

### At 

### the site(s) of herbicide action, species differences In sensitivity often disappear. For example, the Hill reaction In Isolated chloroplasts from different plant species 

### is Inhibited tothe same degree bythe same concentrations of simazine and several other herbicides (van Oorschot, 

### 1976). Differential resistance of plant species to hydrocarbon ols has also been observed (Baker, 

### 1970}. In the

### case of the Umbelliferae, cell membranes have Inherent high resistance to penetration by oils (van Overbeek and Blondeau, 

### 1954).


### It Is worth noting that plants contain a bewUdering variety of organic compoundsthat are toxic to animals. Most ofthese are believed to 

### be evolved, qualitative

## or quantitative, defenses

**aga~nst** herbivory. Interestingly, many ofthese are known phytotoxins, Including organic acids and phenols (Duke, 

### 19n). This fact clear1y indicatesthat many plants already possess mechanisms to detoxify some priority air pollutants.



### POTENTIAL EFFECTS 

### ON PLANTS Ecological Effects


### When photosynthesis and respiration are Inhibited, orATP synthesis uncoupled from metabolism, the

### whole-plant 

### reaction 

### should be reduced growth and 

### reproduction. Energyallocated to alleviating 

### the stress

### of chronictoxin uptake mayalso reduce

### the plants ablityto produce defensive chemicals. Inhibition 

### of root water or 

### ion uptake may increase allocationto roots atthe expense 

### cA 

### shoots. Together, these processes lead to

### lesser competitive ability ofaffected species. Except near 

### point sources oftoxic organics, these effects mayoccurgradually as small 

### but



### 85continuous atmospheric Inputs accumulate. Ultimately, shifts 

### In species composition and dominance may 

### become apparent at the plant community level.

Justwhich species may suffer most 

### Is largely a matter

### of speculation. For

### those organics that readily cross the root endodermls, rates 

### oftranslocation, and 

### hence

### of bioaccum&Jation, may be higherfor plants with greatertranspiration rates 

## O.e., Inherently smaller stomatal resistances). These tend to be ear1y 

### successionaJ species with

### fast growth rates and 

### among late-successional species that are shade Intolerant. Conifers have

### the highest stomatal res!stances

### d any major plant lifeform (Komer et 

### al., 1979), yet they also have exceptionally

### thick, 

### waxy cuticles Intowhich organics may be absorbed. The major route 

### ofentry, foliage vs. roots, 

### oforganics COIJd play a pivotal role In determining the relative resistances 

### ofdifferent plant

### taxa.
Interactions with other Pollutants
Many organics are weak ack:ts, and their lipophUicity

### Is greater In the unionized form. Penetration ofweak-acid herbick:tes through cuticles Increases as solution 

### pH decreases (Fogg, 1948; Sargent and Blackman, 1962; Bukovac, 1976). This phenomenon probably accountsforthe enhanced phytotoxicity of nitrophenols and organic ack:ts at low 

### pH (Simon and Beevers, 1951; Simon et 

### al., 1952). 

### As a result, there Is a strong possibilitythat ack:tifled wet deposition Increasesthe phytotoxicity

### af organics by enhancing uptake (Mullen, 1986). Biogenic monoterpenes present an interesting case. Uke anthropogenic VOCs, they contribute to the photochemical formation of ozone and PAN (Lurmann et 

### al., 1983; Trainer et al., 1987; Chameides et 

### al., 1988) that have been shown unequivocallyto reduce photosynthesis and growth 

### of crop and tree species (Reich, 1987). Wagner et al. (1989) have hypothesized that ozone penetrates the mesophyll 

### ofconifers, increasing membrane permeability and liberating monoterpenes stored in secretoryvesicles. Inthe presence ofozone, monoterpenes promote the oxidation of sulfur dioxideto sulfate, possibly causing local enhancement 

### of acid depositiontoforests (Stangl et al., 1988).

Interactions between different types 

### ofgaseous pollutants are well documented (Ormrod, 1982). Becauseterrestrial plant communities are receMng chronic Inputs of possibly hundreds of different organic compounds, It 

### Is possible

### thatthe overall effects In combination are additive, more than additive, orless than additive.



### 86CONCLUSIONS

Thousands of organic compounds are released Into

### the atmosphere each year by human activities, induding pesticides, aliphatic and aromatic hydrocarbons (both halogenated and unhalogenated), polychlorinated biphenyls, and phthalate esters. These are transported long distances and reach natural vegetation via wet and drydeposition. 

### Depositionftuxes 

### and velocities have been characterized for only a few organics 

### In a 

### few geographic areas.

The potential for plant uptake and bioconcentration 

### d organics 

### is high and correlated with octanol-water partition coefficients. Greatertranspiration rates produce greater

### root uptake. Foliar uptake ofvapor-phase organics has received little

### attention. Translocation patterns differ among organic compounds. Metabolic detoxifK'.atlon plays a major role 

### In plant resistance, 

### but has been well characterized onlyfor pesticides.

With few exceptions, the modes 

### claction 

### clorganics In plants are well-known only for herbicides. A variety of effects by herbicides, usually 

### but

### not always Inhibitory, have been observed on plant growth and morphology; photosynthesis, respiration, and transpiration; cell membranes and ultrastructure; translocation; and respiratory, photosynthetic, and intermediate metabolism. Many of these same effects have been observed with nonherbicide organics. I found no studies on population-, community-, or ecosystem-level effects ofairborne organics.
Relevance of Previous Work



### As the analysis 

### ofthe PHYTOTOX database indicated, there 

### is only one class 

### of organics

- herbicides

- for which the physiological effects on plants are relatively well known. This 

### is hardly surprising, because their purpose 

### Is to kill plants, especiallyweeds. Although 

### It would

### .be desirable to know more about nonherbicide organics, existing knowledge of herbicide effects 

### Is helpful In predicting the impacts of organics In general on terrestrial vegetation. For example, herbicides are at times applied aerially to crops or forests, with consequent downwind drift ontoadjacent natural plant communities. 

### Some herbicide precursors (e.g., 2,«fichlorophenol,

### used to make 2,4-0, and maleic anhydride, 

### used to synthesize pyrldazines) are on

### the EPA's Toxic Release 

### Inventory (U.S. EPA, 1989). Point releases 

### of

### these, and

### cithe finished herbicidesthemselves, 

### from sites 

### clmanufacture may affect natural vegetation. A few herbicides have 

### other human sources besides pesticide manufacture and use. For example, DNP, DNOC, and other nitrophenols are produced as by-products 

### clsmogforming reactions. Finally, 

### the observed correlations between 

### plant bioconcentration or modes of action and 

### the physicochemical properties 

### ci herbicides permit general predictionsto be made concerning 

### the phytotoxic effects 

### of nonherbicide organics.



### 87Nevertheless, 

### the literature emphasis on herbicides 

### poses many obstacles to understanding potential phytotoxicity

### c:K airborne organics. One obstacle 

### is that

### the conditions underwhich herbicides are applied to plants

- high

### concentrations rNer 

### shorttime periods

- are quitedifferent from 

### those encountered by natural 

### vegetation

- 

### low concentrations In a repeated orcontinuous manner. Significant differences between acute and 

### chronic exposures to

### the majorairborne pollutants have been demonstrated (Lefohn and Runeckles, 1987). 

### Thus, extrapolationfrom acute agricUtural doses to chronic natural vegetation doses may be unwarranted. 

### Another dlfficUty 

### is

### the extremely high concentrations

### ci organics 

### used 

### In most dose-response

### experiments. Forexample, solution concentrations 

### d 103to 101 ng/Lare frequently encountered 

### In phytotoxicity studies. Comparethese with the concentrations In Table 1.

The 

### best use that we may

### beable to make

### d the existing literature is to rankthe likelihood of plant uptake of organics according to

### thevapor pressures, K_values, and half-Uves in 

### soU ofthe organics (Ryan 

### et al., 1988; Travis llnd Hattemer-Frey, 1988).

RECOMMENDATIONS

The most critical areas in 

### need offurther knowledge are: (1) spatial and temporal patterns of atmospheric concentrations and wetjdrydeposition rates; (2) rates 

### d uptake by roots from 

### soU, and ofvapors and wet deposition by shoots; (3) translocation patterns; (4) physiological effects from the whole-plant tothe subcellular level; and (5) modes ofaction. In addition, much more emphasis needs to 

### be placed on nonpesticide organics and on native, nonagricultural species growing in natural environments. In all such work, we must use acute or chronic doses that bridge the range of exposures actually occurring In natural ecosystems.
Some soecific suggestions are as follows.
(1) Upgrade routine air, aerosol, and precipitation monitoring networks (e.g., National Atmospheric Deposition Program, National

### Dry Deposition Network) 

### to measure concentrations

### d at least 

### the 

## most common and highly concentrated 

### organics. (2) Characterize drydeposition tovarious plant communities. Traditional direct measurement techniques- flux-gradient and eddycorrelation (Hicks, 1986) -are diffiCult dueto

### thevery low concentrations 

### d most organics. However,

## new advances 

### In lasertechnology- FTIR, lidar, tunable diode lasers

- hold promisefor use oftheflux-gradient technique in the nearfuture.



### 88(3) Develop methods to measure 

### short-term uptake 

### ciorganics byplant 

### shoots. Thesewould

**com~ement** 14

### Cwork by distinguishing 

### between cuticWlrand stomatal 

### absorption, and would permit scaling-up 

### of

**leaf~evel** uptake to entire 

### canopies 

### In Inferential methods 

### ciestimating drydeposition (Hicks, 

### 1986). 

### The technological challenge

### ofgenerating and measuring 

### low 

### but stable concentrations 

### is great, 

### butthepotential 

### gain 

### In predictive capability 

### should be worth

### the effort.


### (4) 

### Conduct experiments on

### dose-response relationships 

### ofwhole plants growing in native soils, Including growth, allocation, morphology, water relations, carbon assimlation, 

### and nutrition. Growth chamber, continuously stirred tank reactor 

### (CSTR), and open-top chamber studies, in order, would provide increasing realism 

### In terms

### ofenvironmental conditions.
(5) Determine the cellular;subcellular modes 

### of action 

### ofvarious classes 

### of organics. Previous work with herbicides suggests thatvirtually everytranslocation and metabolic process Is worthy 

### of investigation.
(6) Measure dose-response relationships for 

### species representative 

### ciother major life forms of terrestrial

**~nts** besides crops: annual and biennial weeds, perennial herbs, ferns, evergreen and deciduous shrubs, evergreen and deciduous hardwoods, and conifers.


### (7) Develop sensitivity rankings based on absorbed rather than external dose. This approach has yielded better predictive capability for major gaseous air pollutants (Reich, 1987). Because organics vary so widely in their lipophRicity, even within similar structural classes, relationships between external dose and response for one organic are unlikely to

**ap~y** to other organics.



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