_m

New Jersey Geological SurveyGeological Survey Report 20

Temporal Variations and Sources of Pb, Cd, Cu, Ni, Fe, and Mn inShallow Ground Water of the McDonalds Branch Basin,

Lebanon State Forest, Burlington County, New Jersey

byIlham Demir

New Jersey Department of Environmental ProtectionDivision of Water Resources

Geological SurveyCN-029

Trenton, New Jersey 08625

1989

ABBREVIATIONS

A.U. absorbanceunit Cd cadmium

DOM DissolvedOrganicMatter Cu coppermeq milli-equivalent Fe ironp.g microgram Mn manganeseu.m micrometer Ni nickelnm nanometer Pb leadPVC polwinyl chloride C02 carbon dioxideZPC zero pointof charge HN03 Nitricacid

0 Oxygen

CONVERSION FACTORS

Readerswho preferto use inch-poundunitsinsteadof the SI (metric)units usedin thisreport may use the followingcon-versionfactors,

Multiply bv to obtainMillimeter(ram) 0.03937 inch On.)centimeter (cm) 0.3937 inch (in.)

meter (m) 3.281 feet (ft)kilometer(km) 0,6214 mile (mi))

square kilometer(kin2) 0.3861 squaremile (mi2)gram (g) 0,03527 ounceavoirdupois

(oz avdp)

GeologicalSurveyReports(ISSN:0741-7357)arepublished by the NewJerseyGeologicalSurvey,CN-029, Trenton,NJ 08625, This report maybe reproduced in whole or part providedthat suitablereference to thesource of the copied materia_is provided.Additionalcopiesof this andother reports maybe obtainedfrom:

Mapsand PublicationsSalesOfficeBureauof RevenueCN-402Trenton,NJ08625

A pricelist is available on request.

Useof brand,commercial, or trade names is for identificationpurposesonlyand doesnot constituteendorsementby the NewJerseyGeologicalSurvey,

CONTENTSpage

Abstract ................................................................................ 1Introduction ........................................................ ..................... 1

Study area .......................................................................... 2Purpose and scope ................................................................... 3Acknowledgments .................................................................... 3Methods of investigation .............................................................. 3Presentation of data .................................................................. 3

Seasonal and other differences in concentrations ............................................. 4Complexation with organic matter .......................................................... 4Adsorption and pH ...................................................................... 7Trace metals ............................................................................ 8

Lead ............................................................................... 8

Cadmium ........................................................................... 8Copper ............................................................................. 8Nickel .............................................................................. 9Iron ............................................................................... 10Manganese ......................................................................... 11

Conclusions ............................................................................ 12Literature cited ......................................................................... 12

ILLUSTRATIONS

Figure 1. Map showing location of McDonalds Branch basin and sampling sites ................... 22-7 Graphs showing seasonal variations of metals in precipitation and of metals

and dissolved organic matter in ground water, McDonalds Branch basin

2. Lead and dissolved organic matter .............................................. 93. Cadmium and dissolved organic matter .......................................... 94. Copper and dissolved organic matter .......................................... 105. Nickel and dissolved organic matter ........................................... 106.'Iron and dissolved organic matter ............................................. 117. Manganese and dissolved organic matter ....................................... 11

TABLES

Table 1. Mean concentrations of six trace metals in blanks and in ground water

from MeDonalds Branch basin, June 1978 - March 1979 .............................. .- 52. Mean concentrations and ranges of six trace metals, DOM, and pH of

precipitation and ground water in the basin, June 1978 - March 1979 .................... 53. Differences between summer and winter concentrations in precipitation

from the basin shown by T' and V values ........................................... 64. Differences between summer and winter concentrations in ground water

from the basin shown by T' and V values ............................................ 65. Differences between concentrations in ground water from organic soil

and from mineral soil in the basin shown by T' and V values ........................... 66. Correlation coefficients between various constituents in precipitation and ground water .... 7

APPENDIXES

Appendix 1. Trace metal levels in ground water .............................................. 152. Trace metal levels in precipitation .............................................. 19

Temporal Variations and Sources of Pb, Cd, Cu, Ni, Fe, and Mn inShallow Ground Water of the McDonalds Branch Basin,

Lebanon State Forest, Burlington County, New Jersey

by Ilham Demlr

ABSTRACT

Concentrations of six trace metals in shallow ground water of the McDonalds Branch basinwere measured for 10months fromJane 1978to March 1979.The results indicate that gignificantamountsof the dissolved Pb, Cu, Ni, andFe are present in shallow ground wateras metal-organiccomplexes. Mean summerconcentrations ofPb, Cu, Fe, Mnand H were significandy higher thanthe mean winter concentrations, apparently due to increased production of dissolved organicmatter (DOM), greater concentrations in precipitation,evapotranspiration,and, in addition, forFe and Mn,higherrates of geochemicalweathering in snmmer. Mean Cd concentration ingroundwater was also higher in summer than in winter although Cd concentration in the snmm_rprecipitation did not differsignificantlyfrom that in the winter precipitation. Apparently Cd isleached into groundwater withoutcomplexing withDOM, andrainorleaching of Cd bound withinsoil material probably occurs, especially in summer. Pb in ground water is supplied almost en-tirelyby precipitation. Atmospheric Cu and Ni, together withevapotranspiration, also appear tobe sufficient to account for Cu and Ni concentrations in ground water. The major source of Feand Mn in shallow ground water is geochemical weathering.

INTRODUCTION

Under natural conditions trace metals enter two trace metals (Fc and Mn) transported toground-water systems through atmospheric some northern Minnesota lakes stay in solutioninput and decomposition of rocks, sediments, owing to the higher concentrations ofhumic andand organic matter. However, especially in in- tannic acids and lower alkalinifins of the lakednstrialized countries, human activities such as waters (Williams and others, 1974). Increasingconstruction, mining,smeltingand processing of human activity appears to be the cause of in-metallic ores, and combustionof fossil fuels have creasing trace metal concentrations in the con-substantially increased the flux of trace metals temporary lake-bottom sediments of Lakeinto the atmosphere and into aquatic environ- Washington in Washington State (Schell andments. Previous studies (Lazrus and others, Barnes, 1974) andsome California lakes (Chow,1970; Nriagu, 1978; Lantzy and McKenzie, 1978).

1979; Swanson and Johnson, 1980) suggested Reliable sampling procedures and analyticalthatin manyplaces atmospherically-borne trace techniques for studying trace metals in naturalmetals are derived primarily from human ac- waters have been developed only wilhin the lasttivities. Elsenreich and others (1986)demonstrated that atmospheric fluxes of Pb to decade or so. The previously published datashouldtherefore be used withextreme care. Forboth urbanand rural areas in the United States

correlate positivelywith Pb used in gasoline, example, a large proportion of ground-watersampleswere taken from steel-cased productionAtmospherically-borne trace metals eventual- and observation wells. Samples from such wells

ly return to Earth's surface, and subsequently are vulnerable to contamination caused by reac-they are either held by soils and rocks or tion between steel and water.

transported in water depending on ambient In this study, levels of six trace metals, Pb, Cd,physical and chemical conditions. Streams andprecipitation entering northern Lake George in Cu, Ni, Fe, and Mn, in ground water collectedthe Adirondack Mountains lose part of their near McDonalds Branch, a stream in Lebanon

State Forest, NewJersey,were monitored duringtrace metals to the lake sediments. Elsewhere, the period June 1978-March 1979to investigate

1

<--_\\\ _/ ".,,,,:\ _'_

,+++++- • 7 i" '

- r, <_ L+-+ .++BROWNSM_LL,_UAI_ J,,_.,,..<,,+,, ( / _] - ", '? wo_mA.S,E_uAo ,

• < ) "+ ,

]...,o..+.<<,

Z " 6

-- ._< 0 .5 mi

; I Ilkm

l_'igure|. Location of McDonalds Branch and sampling sites.

their seasonalfluctuations.The resultsare inter- areas,weil-dralned mineral soils (()uartzipsam-prctcd in terms of atmosphcriclnput, fluid-rock ments and Hap|udults soils (Swanson andinteractloa, andblochemJca]actlvity. Johnson, ]980) 50 to 100 cm thlck) have

developed. The soil pH rangns from 3.6 to 5.0Study Area (Marklcy, 1979). Although soil particles are

McDonalds Branch drains a small (6 km2) generally coated with iron oxides, bleaching ofpristine basin in the Pinelands in Lebanon State surface horizons under an organic matter layer,

Forest in south-central New Jersey, about 56 km 10 cm or less in thickness, is common. Histosolseast of Camden. The Branch is a small head- (organic soils) have developed in lowlands

waters brook that is tributary to Rancocas Creek, (Swanson and Johnson, 1980) where the waterwhich in turn flows into the Delaware River table is very close to or at the land surface and

(fig. 1). The wells were situated close to the thick, finclydividcdorganicmuckandpeatover-Branch, at elevations of about 35 - 41 m (115 to lie the Cohanscy Sand. Top organic matter135 ft) above sea level. McDonalds Branch horlzonsarediscontlnuonsandareburnedeverymeanders northwestward in the study area for a 2 to 5 years to reduce the hazard of forest firesdistance of about 3 km. and to control the forest composition. There is

little mixing of the organic horizon and mineralThe basin is underlain by the Cohanscy Sand matter of the soils owing to inhibition of soil-or+

of Mincone (upper Tertiary) age (Zapecza, gaulsm activity by,low soil pH. Mineralweather-1984)+TheCohanscyisunconsolidatcd, about30 ing is not extensive because mineral horizons

meters thick, and consists of gravelly sand, fine consist mostly of iron-oxide-coated silica par-to coarse sand, and some clay lenses. In upland ticlns. As a rcsult these soils have a low ion cx-

change capacity (0-4 meq/100 g) and a low buf- augers and a sledge hammer in pitch pinefering capacity (Markley, 1979; Douglas and lowland mineral soil. Ground-water samplesTrela, 1979). Both the ground water and stream wereusually,though not always, collected oncewater arc very soft, ranging from 15 to 35 rail- everytwoweeks (see appendix 1) usingavacuumligrams per liter (rag/L) in dissolved solids coo- pump; they were stored in acid-washedcentration (Swanson and Johnson, 1980). Fe polyethylene bottles. The 10-month collectionmight be introduced to ground water from un- period extended from June 1978 to March 1979.derlying metalliferous clay of Cretaceous and Before sampling, water levels in the wells wereTertiary age andfrom glauconitic layers (Means measured and the wells were pumped down toand others, 1981). considerablybelow the top of the lower meter of

perforated casing. After samplingthe wells werePurpose and Scope emptied. The wells were capped throughoutthe

This study was conducted by the author, af- periodof studyexcept duringsampling.All sam-filiated withthe Illinois State Geological Survey piing equipment and bottles were transported(615 E. Peabody Drive, Champaign,IL61820) at and stored in plastic bags.

time of publication, in partial fulfillment of the The pH of the samples was determined withinrequirementsfor the M.S. degreein the Depart- 2 to 4 hours after collection using glassment of Geology at the University of Pennsyl- electrodes. After the pH measurements, thevania in 1978-1979. Publication by the New samples were filtered using 1-_m Nuclepore-Jersey Geological Surveyis based on the factthat membranefiltersto removesuspended particles.the studysite isin NewJersey and the report con- The filtered samples were acidified with con-tains new factual data and interpretationwhose centrated HNO3 to prevent precipitation of dis-significance extends beyond the boundaries of solved substances during a storage time of i toLebanon State Forest. 10 days.The sample-to-acid ratiowas 10 to 1.

Acknowledgments Dissolved organicmatterconcentrations of theThe authorwould like to thankArthur Johnson samples were estimated in terms of absorbance

and Robert Giegengack, both at the University units (A.U.) at 430 nmon a Hitachi Model 100-of Pennsylvania,for their support and guidance 10 spectrophotometer using the procedure ofduring the course of this research; and Deborah Gjessing (1976). Trace element concentrationsLord, U.S. Geological Survey,Dr. David Crerar, were determined using a double-beam Perkin-

Elmer atomic absorption spectrophotometer,Princeton University, and Chen-Lin Chou, Il-linois State Geological Survey, for critically Model 372, with graphite-furnace atomizer.reviewingthemanuscript.Theauthorwouldalso Standards were prepared using stream andlike to thank I.G. Grossman, New Jerscy precipitationwatersfromthestudyarea. BlanksGeological Survey, for carefully editing the were prepared using triple deionized water andmanuscript, were periodically transported to and from the

sampling sites to determine the effect oftransportation, if any, on the samples. A corn-Methods of Investigationparisonof the valuesof blanks andground-water

Six wells were installed in the basin (fig. 1) to samples is shown in table 1. Immersion of a piececollect shallow ground-water samples. The wells of PVC-cased pipe in deionizcd water in thewere cased to a depth of 1.5-2.0m with ASTM- laboratory for 24 hours indicated no detectablelisted rigid PVC 3.5 cm in inside diameter, trace metal leaching from the pipe. Materials,Before installation,the PVC tubes were sealed methods, frequency of collection, and qualityand pointed at the bottom end, perforated in control for the precipitation samples are giventheir lower meter with0.5-mm holes, and acid- by Swanson (1979). The basic data are in thewashed. Three of thewells (nos. 3, 4, and5) were M.S. thesis, copies of which are on file in thein relatively well drained mineral soil and three main library and the geology library of the(nos. 1, 2, and 6) were in mostlywaterlogged or- Universityof Pennsylvania.ganic soil. Wells I and 2 in cedar swamp, well 5

in pine lowland adjacent to a hardwood swamp, Presentation of dataand well 6 in the hardwood swamp, were

Data obtained forground water and preciplta-emplaced by forcing them down manually in thetion from June 1978 to March 1979 are given in

soft soils. Wclls 3 and 4 were sunk using soil appendixes 1 and 2. Range, mean, and standard

3

deviation of each measured parameter for the Trace metal and DOM concentrations insampling period arc given in table 2 for both precipitation and ground water are plottedground water and precipitation. Results of t- against time in figures 2-7. Each data point forstatistics analyses (to determine differences ground water in the graphs is a mean value of allamong data sets) are given in tables 3-5, and a wells sampled. Figures 2-7 do not show Marchsummary of correlation analyses of the ground 1977values forprecipitation.These values, how-water and precipitation data is given in table 6. ever, are given in appendix 2.

SEASONAL AND OTHER DIFFERENCES IN CONCENTRATIONS

Table 3 shows that concentrations in precipita- ved among Pb, Fe, Cd, Ni, Mn, pH, and Cu.

tion were higher during summer than during Mean concentrations in the precipitationwinter for Pb, Cu, Fe, and H, whereas seasonal(table 2) and 50-percent evapotranspiration

differences for Cd, Ni and Mn were insignificant. (Robertson, 1973) can account for mean Pb, Cd,Table 4 shows that concentrations in ground Cu, and Ni concentrations in the ground water.water were higher during summer than during However, contribution of precipitation to thewinter for Pb, Cu, Cd, Fe, Mn, and H, whereas concentrationsof Feand Mnin thegroundwaterthe seasonal difference for Niwas not significant, is relatively small.Table 5 shows that concentrations of dissolved

Fe and Mn were substantially higher in the The following section discusses cemplexationmineral soil than in the organic soil, whereas and adsorption as possible mechanisms ofother elements did not differ significantly. Table transport and retention of trace metals. A sub-6 shows that Pb, Cu and Fe correlate positively sequent section deals with the temporal varia-with DOM in the ground water. Ni also corre- tion of each element in relation to atmosphericlates positively with DOM but only for the input, transport, retention, and geochemicalground water within the mineral soil. For weathering.precipitation, positive correlations were obser-

COMPLEXATION WITH ORGANIC MATTER

Many investigators (among them Means and derived by leaching of decaying plant materialsothers, 1981; Gjessing, 1976; Marshall, 1964; onthe forest floor. Means and others found thatSchnitzer and Skinner, 1967; Davis, 1984) have in the Pinelands, fulvic acid has a greater totalindicated that DOM can mobilize trace metals acidity and therefore metal binding capacityin aquatic environments by forming soluble or- than humic acid. Correlation between DOM andgano-metaUic complexes. However, it is less cer- Pb, Cu, Fe, and Ni (table 6) suggests that thesetain whether or not a positive correlation metals formorgano-metalliccomplexeswithful-between metals and DOM always indicates com- vie and perhaps also with humic acid, theplexation. Fox (1984), for example, reported that predominant organic compounds in most soilsdissolved humic acid and soluble iron appear to and waters of the Pinelands. Once in the solu-be chemically unassociated in estuaries despite tion, these complexes may release the metals iftheir coincidental removal. On the other hand, pH decreases and ionic strength increasescomplexation between organic acids and trace (Gjessing_ 1976). The ionic strengths were notmetals in soils and ground waters is well estab- determined for this study. The effect of decreas-lished (Stevenson and Ardakani, 1972; Stone iugpHisdetectedonlyforthereleaseofPbfromand Morgan, 1984). DOM, as indicated by a negative correlation be-

Using elemental analysis, functional group tween Pb and pH (table 6). Relatively weaktitrations, infrared spectrophotometry and gel DOM-metal correlations and the effect of un-filtration chromatography, Means and others known ionic strength apparently mask the rela-(1981) characterized DOM, consisting largelyof tion between pH and the release of other metalshumic and fulvic acids, in the Pinelands stream from DOM. Complexation with DOM is, then,waters. These organic materials are largely important in moving Pb, Cu, Fe, and perhaps Ni

Table 1. Mean concentrations of six trace metals in blanks and in ground water from McDonalds Branchbasin, June 1978 - March 1979.

Mean blank Number of Standard Mean concentration

Element concentration blanks error in ground water

(re/L) (Feg L)Pb 2 16 0.25 12Cd 0.4 13 0.06 1.2Cu 2 16 0.50 7Ni 3 16 0.50 7Fe 7 16 1.25 440

Mn 3 17 0.70 63

Note: Allsamplesand blankswerefilteredthrough1 panNueleporemembranefiltersand acidifiedwithconcentrated,reagent-grade HNO3.Meanconcentrationsingroundwaterweredeterminedaftersubtractingtheblank.

Table 2. Mean concentrations and ranges of six trace metals, DOM, and pH of precipitation and groundwater in the basin, June 1978 - March 1979.

PRECIPITATION a

Element or Number of Range Mean Standard

constituent samples deviationpH (units) 29 3.3-4.5 3.77 b 3.90 bPb (lag/L) 29 4-118 23 23Cd (lag/L) 29 < 0.1-5.8 0.5 1.16Cu (I_,/L) 29 1-11 4 3.34Ni (lag/L) 29 1-46 7 9.1Fe (lag/L) 29 6-158 53 46Mn (lag/L) 29 1-112 21 32

GROUND WATER

Element or Number of Range Mean Standardconstituent samples deviationpH (units) 80 2.8-5.4 3.97° 3.66 t'DOM (absorb-

ance unit) 75 0-2.04 0.180 0.36Pb (lag/L) 78 < 1-86 12 16.9Cd (p.g/L) 78 < 0.1-13.6 1.2 2.4Cu (lag/L) 78 < 1-71 7 12.6Ni (I_:,/L) 78 < 1-72 7 10.4Fe (_/I.,) 78 43-2715 440 463Mn (lag/L) 78 5-206 63 44

aFromSwanson(1979).

bCaleulatedusingH+ concentrations.

Table 3. Differences between s-miner and winterconcentrations in precipitationfrom the basin shown byT' and V values.

SUMMER (Juue'78-OcL'78) WINTER (Nov.'78-Mar.'79)

Element or n I X! S12 N2 X2 $22 T' (value V (degreesconstituent (mean) (variance) (mean) (varlam_) oft-distribution) of freedom)

H (mole/L) 16 2-44g104 1.6x10"s 13 0.8x10"* 0.8x10"9 4.8_3a 17DOM(absorbanceunit) ............

Pb (gg/L) 16 29 724.2 13 15 234 L760b 25CA (l_f/L) 16 0.2 0._t 13 0.8 2.81 1.276 13Cu (t_g/l.) 16 5.7 10.8 13 1.8 3.81 3.964" 25Ni (_g/L) 16 8.5 120.9 13 4.5 30.6 1.271 23Fe (gg/L) 16 70 1934 13 32 1658 2.391b 27Ma (tts/L) 16 26 1431 13 15 534 0.963 2.5

Table 4. Differences between s-miner and winterconcentrations in groundwater from the basin shownby T' and V values.

SUMMER (June_78-Oc1.'78) WINTER (Nov.'78-Mar.'79)

Element or nI Xt St2 Nz X2 $22 T' (value V (degreesconstituent (mean) (variance) (mean) (variance) oft-digribution) of freedom)H(mole/L) 48 L41xl04 7.11x10_ 32 0-55x104 2-95x10"9 2-168b 53DOM (absorb

ance unit) 44 0.277 0.200 31 0.041 0.003 3.464' 45Pb (t_/L) 47 18 375.78 31 2 2.58 5.629a 47Cd (rig/L) 47 1.9 8.52 31 0.2 0.065 3.975a 47Cu (lag/L) 47 10.8 228.19 31 L5 3.36 4.174a 48Ni (_g/L) 47 7 115.53 31 6 98.33 0.416 68ICe(ttg/L) 4"1 560 297651 31 259 _659_ 3.4"]3b 61Me (I._g/L) 47 72 2541 31 51 842 Z330b 75

Table 5. Differences between concentrations in ground waters from organicsoil and from mineralsoil inthe basin shown by T' and V values.

ORGANIC SOIL MINERAL SOIU

Element or nI XI SI2 N2 X2 $22 T' (value V (degreesconstituent (mean) (variance) (mean) (variance) oft-dlslribufion) of freedom)H(mole,q,) 42 9.63x10"5 2.4x10"8 38 11.96xi0 "5 6.76x10 "8 0.853 64DOM (absorb

&aceunit) 41 0.165 0.114 34 0.198 0.148 0.391 66Pb (_) 42 13 377.23 36 10 166.58 0.813 72Cd (t_L) 42 L4 6.41 36 1.0 4.93 0.743 76Cu (t_g/L) 42 6 L30.86 36 9 182.47 1.049 69Ni (gg/L) 42 8 176.04 36 6 21.69 0.913 52Fc (glg/L) 42 289 145340 36 616 230601 3.294 ' 66

Mn (rig/L) 42 48 841.9 36 83 2453 3.727 • 55

asi_tificant at p =0.01. Note: For equal variance,

bsignificanl at p = 0.05.

IXl'X2l ( (nl-1)Sl 2 + (N2-I)S2 2) 1/2T" V= nt+N2-2 ;Sp- -1 1 _1/2 ' V

sp(_ + _,

. Sl 2 S22/2For unequal variance: V= ("_ + _"

T = _ . ( Sl!12 ,.S22 ,2

(_1 + _) "n1-'--1 N2-1

Equality of variance was tested using F-dist ribution.

6

Table 6. Correlation coefficients between various constituents in precipitation and ground water.

PRECIPITATION GROUND WATER

n r I1 r

Pb-pH a 29 -0.556 b Pb-pH a 78 -0.258 ¢Ni-pH a 29 -0.487 b Pb-DOM 75 0.682 bFe-pH a 29 -0.476 b Cu-DOM 75 0.427 b

Cu-pH a 29 -0.434 b Fe-DOM 75 0.410 bPb-Fe 29 0.687b Pb-Cu 78 0.354 bPb-Ni 29 0.386 c Pb-Fe 78 0.344 bCu-Fe 29 0.491 b Pb-Cd 78 0.495 bNi-Fe 29 0.464 b Cu-Fe 78 0.368 bMn-Fe 29 0.411 ¢ Ni-DOM ° 34 0.553 b

aealculated using H + concentrations. _ignifieant at p = 0.05.bsignifieant at p = 0.01. only for the ground water of the mineral soil.

in the study area. However, not all of the varia- microorganisms, changing CO2 and 02 levels,tions in metal concentrations are accounted for growing roots, and fluctuation of the water tableby variations in DOM because the DOM-metal are also involved in the mobilization of trace me-correlation coefficients are smaller than unity, tals monitored.Other factors, such as temperature, respiring

ADSORPTION AND pH

Iron oxides are known to be an efficient sink the ground water. Means and others (1981)

for trace elements (Gadde and Laitinen, 1974; found that H + in the precipitation of the

Schwertmann and Taylor, 1977). The Pinelands ecosystem is balanced bySO42". The_mechanism of this retention is moot. Adsorption also found that the maximum atmospheric SO4 "or desorption of H + on the surface- of metal inputs to the basin occurred in summer whereas

oxides results in net surface charge. Adsorption the maximum SO42"output through the streamsof metal ions is probably accompanied by release occurred in winter. Generally lower pH valuesof H + from the surface (Davis, 1984). The zero but higher H + in summer precipitation than inpoint of charge (ZPC) ranges from pH 6.5 to pH winter precipitation (table 3) also indicate10.4 for different oxides of the type (Metal)203 higher + ' " "H input m summer dunng the studywhich includes all Fe3+-oxides (Parks, 1965). period. Apparently, flushing of the atmos-ThepHofgroundwaterinthestudyarearanges pherically introduced H + from upper soil

from 2.8 to 5.4, suggesting that the exchange sites horizons increases in wet months of winter.on Fe-oxides are loaded mostly by H ions. However, in summer, internally generated HTherefore, trace element adsorption on Fe- in the ground water increases due to increased

oxide coatings should be insignificant at these organic acid production, resulting in a lower

low pH values. The very small proportions of the mean pH (but higher mean H + ) value of groundtrace elements that may be adsorbed on Fe- water in summer than in winter (table 4).

oxide coatings may subsequently be mobilized Trace metals may also be adsorbed on silicaand transported by bumic substances within the surfaces (Wilding and others, 1977). A smallaquifer. Vuceta and Morgan (1978) reported amount of surface charge on silica mineralsthat oxide surface hydroxyls and organic matter arises from Si-0 broken bonds and Si-0H bond-compete for the adsorption of metals if organicmatter is not itselfabsorbed on oxide surfaces, ing around particle edges. This type of charge is

also pH-dependent and increases with decreas-

Mean pH value in ground water higher than ing particle size. Leckie and James (1974) indi-that in the precipitation (table 2) indicates that cated that the ZPC may be as low as pH 2-3 forthere is still a geochemical control on the pH of quartz. However, because the silica surface

charge is very small compared to the Fe-oxlde Fe-oxides, metal adsorption by silica surfaces is

surface charge, and because most silica grains in also negligible for this study.shallow aquifers of the Pinelands are coated with

TRACE METALS

lead does not complex with organic matter in aqueous

Dissolved Pb in common geological environ- systems. It thus appears that atmospherically-ments exists as Pb z + in acid solutions if it is not borne Cd and perhaps also a very small amount

complexed with organic matter (Vuceta and of Cd weathered from the soil minerals moveMorgan, 1978). Atmospherically-borne Pb ac- into the ground water as Cd 2+. Mean Cd con-

cumulates chiefly in the soil due to its complexa- centration in the ground water (1.2 _g/L) istion with organic matter (Reiners and others, higher than that in the precipitation (0.5 _g/L).1975; Benninger and others, 1975; Van Hook The greater-than-twofold difference may beand others, 1977; H einrichs and Mayer, 1977; caused in part by cvapotranspiration of about 50Siccama and Smith, 1978). This appears to be percent. Because the concentrating effect oftrue also for the study area because Pb levels in evaporation in summer is likely to be close to thatthe precipitation are significantly higher than in winter in the study area (Swanson andthose in the ground water (table 2), and Pb posi- Johnson, 1980) and because mean Cd concentra-tively correlates with DOM in the ground water tion in summer precipitation is not significantly(table 6, fig. 2). Pb-organic-matter complexes different from tha! in winter precipitation (tableapparently become more soluble and/or Pb is 3), higher Cd levels of the ground water in sum-released from organic matter, thus raising the mer probably result from leaching of a smallconcentrations of Pb in ground water during amount of Cd bound within soil material due tosummer because of decreased pH (increased lower pH, warmer temperature and, according-H +, table 4), increased microbiological activity ly, higher rate of chemical weathering.and higher temperature. Because Fe- and Mn-oxides and quartz do not adsorb Pb under low Copper

pH conditions (Gadde and Laltinen, 1974; Cu and DOM in the ground water are positive-Leckie and James, 1974), Pb adsorption on inor- ly correlated (table 6), suggesting that organicganic phases in the study area, where pH is low layers of soil adsorb and subsequently release Cu(table 2), is unlikely or minimal, in the form of dissolved Cu-organic-matter corn-

Because atmospheric Pb is the source of Pb in plexes. In a study of adsorption of Cu 2 + and

ground water, change in the atmospheric input Cd2 + on alumina and organic matter in aqueouscan cause observable changes in Pb levels in systems, Davis (1984)found that Cu 2+ was par-ground water. A sharp decrease in the mean Pb titioned primarily between the surface-boundcontent of regular-grade gasoline after 1979 (El- organic matter and dissolved organic matter,senreich and others, 1986) and accordingly and that complexation with the surface-bound

decreasing Pb input to the atmosphere may have organic matter was stronger than that with un-reduced the seasonal averages of Pb concentra- covered alumina surface hydroxyls. Trace ele-tion in the ground water following the comple- ment adsorption on inorganic surfaces istion of this study, insignificant in the study area so that mobility of

Cu is apparently controlled by the dissolution-

Cadmium precipitation reactions and by the mobility of or-ganic matter. The Cu in the ground water

Low Cd concentrations, which are about at the appears to be accounted for by atmosphericdetection limit of the method used, make the input and the evapotranspiration of 50 percent.precise determination of its sources difficult, but Mean Cu concentration in the ground water isCd concentrations in the ground water can be ac- higher in summer (table 4, fig. 4) because of in-counted for by precipitation and evapo-

creased mean atmospheric input (table 3, fig. 4)transpiration. There is no correlation between and increased mobility of Cu 2+ due to lower pHCd and DOM in the ground water (fig. 3), a find- (higher H +, table 4).ing consistent with previous investigatiofis(Davis, 1984; Norvell, 1972) showing that Cd

8

Nickel difference between Ni concentration in the

Table 6 shows a correlation between Ni and ground water of the mineral soil and the organicDOM for the ground water of mineral soil but soil (table 5). It seems that other chemicalnot for that of organic soil. At first, this suggests processes mobilize Ni in the study area, and thethat either Ni-orgnnic-matter complexes are un- Ni-DOM correlation may or may not be coin-stable in reduced environments, or Ni probably cidental. The mean Ni concentration in summerprecipitates as an insoluble Ni-sulfide in precipitation is not significantly different from

swamps, because their waterlogged organic soils that in winter precipitation (table 3), and thegenerate significant amounts of HzS, especially mean concentrations in the ground water andin summer. However, mean Ni concentrations of precipitation are similar for the 10-month periodground water for summer and for winter are of study (table 2). It appears then that Ni in the

similar (table 4, fig. 5), and there is no significant ground water is basically supplied by atmos-

11o LEAD e CADMIUM

I00

_.9o _.80

._7o- .__"m

I j I I ;

f. 30 i, /" _. i \ f,. : \ , ; .-..45 _ I , i 9 _ I , ,

LEAD 8 CADMIUM40-

_ Each dltl point Is mean36 . Eec h datl point Is maen

of ell wells sampled, _ 7 of in walls sempia_,

_3o- ,, | 6il

/ '_ _

_," 4k ,.le_-- t" _ .....0 _,, 0 I

0,7 I i i I I i 1 I I 0,7 i i i I I I _ I

"_ DISSOLVED

o o.e - _. DISSOLVEDORGANIC MATTER _ 0.e _\ ORGANIC MATTEREach date _oktt Is mean

-; 0.5 - _ \ Each d_ point I_ mean _ 0.5 _. Of all walls s_mpled, <_ _ I of all walls sampled,

; io., ,r ,

o* ; 0,2 I

/_,. g o., ', ,-,,_lp..4 tl _ 0

' ' I ' ' I:E 0 , JUL 1 AU_ ' SEP OCT ' NOV DEC JAN _FE B _ jU L ] AU Q ' SEp OCT ' NO V DEC JAN _ FEB1978 1979 19_'8 1979

Figure 2. Seasonal variations of lead in prccipita- Figure 3. Seasonal variations of cadmium intion, and of lead and dissolved organic precipitation, and of cadmium and dis-matter in ground water, McDonalds solved organic matter in ground water,Branch basin. MeDonalds Branch basin.

9

pheric input. The chemical factors that control weathering. Thus, Fe in the ground water isthe mobility of this atmospheficaly-berne Ni in mainlygeochemical, not atmospheric, in origin.thesoil of the study area cannot be determined One of the sources of Fe mightbe the underly-with the present data. ing metalliferous clay and glanconitic beds

(Means and others, 1981).A positive correlationIron between Fe and the DOM in the ground water

Fc concentrations in the ground water are (table 6) indicates that another source of Fe ismuch higher than can be accounted for by the reduction and removal of ferric Fe from Feevapotranspiration of precipitation (fig. 6). The compounds in the soil by acidic organic-matter-especially high Fe concentration within the rich waters seeping down from the organicmineral soil (table 5), which contains more Fe layers.This maybe the cause of bleached surfaceoxides, indicates the importance of geochemical horizons below organic-matter layers within the

15., , , I , , I . I 22 -' I i i i21 . /I14 tl

,3 COPPER 20 I I NICKEL19 . it

i6-to 15 - I

14- /

/'J i 10 - j I_'= h 1 / Q 8- I ii" ' l ' E 7- [ '1

,,',,i''t - 7% / I I \., _ II f I / ll_ -llI

24 i 1 , , 19 , , I rI 18-

22 /_ COPPER 17- NICKEL

i 9-_ Il 14 _ 1 12-

o _ ', _='_: ,\

o 0I I

-° °I........-°,o ORGANIC MATTER o o.e _, ORGANIC MATTER)5 I Each data point is mean D 0,5 _ Eich dmtl pc/el is mellt

i JI of iiii wells sllmpled _ iffI of &l/ wlllhl s_mpled.

I _, I

1 ...)3 _ _ _ 0.3 _ I

',j _ ',,,

i°' ":"i " "- ........ "JUL AUG SEP OCT NOV ' DEC I JAN FEB :E 0 ' JUL AUG 81EP OCT NOV DEC [ JAN FEB

1978 1979 1978 1970

Figure 4. Seasonal variations of copper in FigureS.Seasonalvariatlonsofnickelinprecipita-precipitation, and of copper and dissolved tion, and of nickel and dissolved organicorganic matter in ground water, Me- matter in ground water, McDonaldsDonalds Branch basin. Branch basin.

10

mineral soil, although at least some of this Fe is (table 5). These relationships indicate thatredeposited in the B horizon, geochemical weathering is the major source of

Mn in the ground water, and that atmosphericManganese input contributes somewhat less. Dissolutioli of

There is no correlation between Mn and DOM Mn-oxides by fulvic acid and other organics hasin the ground water, and the mean ground-water been demonstrated in the laboratory (Stone andconcentration exceeds the mean precipitation Morgan, 1984).This might also be occurring inconcentration by threefold (table 2). Mean Mn the Pinelands to some extent. However, simpleconcentration in ground water is higher in sum- dissolution-precipitation reactions that do notmer than in winter (table 4, fig. 7), but seasonal involve organic matter apparently are dominantdifference for precipitation is insignificant for mechanismscontrollingthemobilityofMninthethis element (table 3, fig. 7). Furthermore, mean study area. In summer, increased chemical ac-Mn concentration for the mineral soil is sig- tivity due to warmer temperature acceleratesnificantly higher than that for the organic soil weathering and mobilization of Mn.

160 i i J I I 120 I150 I i I I I I

^ t3o MANGANESEJ

_,,2o. _=80 ._qI

o,oo.! ,,o"-- eo I I / - /

co. I , I , I / I _ 5o I

£ 50- _ c 40..o '-' \ / , ', - ,,,, /, , ,''

2O-,o_ _",/ \.,v.e"_' ,o _, ...,_. / L,

z.5 L I 12o J I

1.4- IRONt.3 - / _ i _o. MANGANESE

J: I Eac h data I)otn! is mean /__. 1.2 - I _. Each data point IS mean

v I00 . \ °l ell Wells sampled.1.1 - ii of ell wells s,mpled.

_. i.o- I _ I IO,g- / _ 90-

I 3¢ pI _ co-°,8- I

• 0.7- i _ I

0.2- _/ _.__._ / / :_ 50- / \_ 0.1

I 40.

l -\ D, SO'VED °' ..... ' '

DISSOLVEDo.e- ORGANIC MATTER o 0.e -. w _ ORGANIC MATTER

i0.5 __ I E#Ch dte_a poinl IS mean _

of ,tl wells sampled. _ 0.5 - _ Each d,t, _olnt is re,an/ <_ /'m of ,11 well, scrupled.

0.4 I

I _ 0.4 I

o=o.3-]', / _

E t _l o=o 0,1 -'_\_ _ 0.1 /.C"_'-..

=: 0 'JUL ' AUG SEp ' OCT t_OV ' DEC I nAN FEB :_ 0 _,. "-.,,__ .____,_a1978 1979 JUL _ AU G ' SEp ' OC T ' NOV ' DE C [ JAN ' FEB '

1976 1979

Figure 6. Seasonal variations of iron in precipita- Figure 7. Seasonal variations of manganese intlon, and of iron and dissolved organic pretfipitation,and of manganese and dis-matter in ground water, McDonalds solved organic matter in ground water,Branchbasin. McDonalds Branch basin.

11

CONCLUSIONS

Pb, Cth Ni, and Fe arc leached from soils the ground water originates mainly fromand/or sedimentaryrocks into the ground water geochemical weathering of soil and sedimentaryboth as organo-metallic complexes and as dis- minerals. Atmospherically-borne Ni suppliessolved ions in the McDonalds Branch Basin, most of Ni in the groundwater. Cd, primarilyat-Pinelands, New Jersey. The leaching of Pb, Cu, mospbcric,does not complex with organic mat-Fe, and Mn increases in summer owing to in- ter,butisleanhedintothegroundwaterasCd 2+.creased microbiological activity and chemical Geoehemicalweatheringprobablycontributnsaweathering. Atmospherically-borne Pb, almost very small mount of Cd to ground water, espe-the only Pb source in the ground water, is large- cially in summer. Like Cd, Mn does not appearlyaccumulated by the forest floor, owingto corn- to complex with organic matter; Mn in theplexation withorganic matter. Precipitationand ground water is supplied by geochemicalan evapotranspiration rate of 50percent account weathering of the soil material and, to a lesserfor Cu concentrations in the ground water. Fe in extent, by atmospheric input.

LITERATURE CITED

Benninger, L.K., Lewis, D.M., and Turekian, Gjessing, E.T., 1976, Physical and chemicalK.K., 1975, The use of natural Pb-210 as a characteristics of aquatic humus: Annheavymetal tracer in the river-estuarine sys- Arbor, MI, Ann Arbor Science, 120p.

tem, in Church, T.M., editor, Marine Groet, S.S., 1976, Regional and local variationschemistry and coastal environment: Am. in heavymetalconcentrationsofbryophytesChem. Soe, Symp. Ser., no. 18, p. 201-210. in the northeastern United States: Oikos, v.

Chow, T.J., 1978, Lead in natural water, in 27, p. 445-456.

Nriagu, J.O., editor, The biogeochemistry of Heinrichs, H., and Mayer, RJ., 1977, Distribu-lead in the environment, Part A, Ecological tion and cycling of major and trace elementscycles: New York, Elsevier Press, p. 185- in two central European forest ecosystems:218. J. Environ. Quality. v. 6, p. 402-407

Davis, J.A., 1984, Complexation of trace metals Lantzy,RJ., and Mckenzie, F.T., 1979, Atmos-by adsorbed natural organic matter: pheric trace metals: global cycles and as-Geoehim. Cosmochim. Acta, v. 48, p. 679- sessment of man's impact: Geochim.691. Cosmochim. Aeta, v. 43, p. 511-525.

Douglas, L.A., and Trela,JJ., 1979, Mineralogy Lazrus, A.L., Lorange, Elizabeth, and Lodge,of Pine Barrens soils, in Forman, R.T.T.,editor, Pine Barrens: Ecosystem and J.P., 1970, Lead and other metal ions in

United States precipitation: Environ. Sci.Landscape: New York, Academic Press, p. Technol., v. 4, p. 55-58.95-109.

Elsenreich, S.J., Metzer, N.A., and Urban, N.R., Leckie, J.O., and James, R.O., 1974, Controlmechanisms for trace metals in natural1986, Response of atmospheric lead todecreased use of lead in gasoline: Environ. waters, in Rubin, AJ., editor, Aqueous en-

vironmental chemistry of metals: AnnSci. Technol., v. 20, p. 171-174. Arbor, MI, Ann Arbor Science, p. 1-76.

Fox, L.E., 1984, The relationship between dis- Markley, M.L., 1979, Soil series of the pine bar-solved humic acids and soluble iron in es-tens, in Forman, R.T.T., editor, Pine Bar-

tuaries: Geochim. Cosmocbim. Acta, v. 48, rens: Ecosystem and Landscape: NewYork,p. 879-884. Academic Press, p. 81-93.

Gadde, R.R., and Laitinen, H.A., 1974,Studiesof heavy metal adsorption by hydrous iron Marshall, C.E., 1964,The physical chemistry andand manganese oxides: Anal. Chem., v. 46, mineralogy of soils, v. 1: New York, Johnp. 2022-2026. Wiley, 388p.

12

Means, J.L., Yuretich, R.F., Crerar, D.A., Stevenson, FJ., and Ardakani, M.S., 1972, Or-

Kinsman, DJJ., and Borcsik, M.P., 1981. gauic matter reactions involvingHydrogeochemistryofthe New JerseyPine micronutrients in soils, in Mortvedt,Barrens: Trenton, NJ, New Jersey Geol. J.J.,Giordano, P.M. and Lindsay, W.L.,Surv., Bull. 76, 107p. editors, Mieronntrients in agriculture,

Norven, W.A., 1972, Equilibria of metal chelates Madison, Wl, Soil Scl. Soe. Am., p. 81-114.

in soil solution, in Mortvedt, JJ., Giordano, Stone, A.T., and Morgan, JJ., 1984, ReductionP.M., and Lindsay, W.L., editors, anddissolutionofmanganese(IIl)andman-Mieronutrients in agriculture: Madison, WI, ganese (IV) oxides by organics, 2, Survey ofSoil Sei. Soc. Am., p. 115-170. the reactivity of organics: Environ, Sei.

Nriagu, J.O., 1978, Lead in the atmosphere, hi Technol., v. 18, p. 617-624.

Nriagu, J.O., editor, The biogeochemistry of Swanson, K.A., 1979, Trace metal budgets for aleadintheenvironment:NewYork, Elsevier forested watershed in the McDonalds

Press, p. 137-184. Branch basin, New Jersey: M.S. thesis,

Parks, G.A., 1%5, The isoelectric points of solid University of Pennsylvania, Philadelphia,PA, 97p.oxides, solid hydroxides and aqueous

hydroxy complex systems: Chem. Rev., v. 65, Swanson, K.A., and Johnson, A.H., 1980, Tracep. 177-198. metal budgets for a forested watershed in

Reiners, W.A., Marks, R.H., and Vitousek, the New Jersey Pine Barrens: Water

P.M., 1975, Heavy metals in subalpine and Resources Res., v. 16, p. 373-376.

alpine soils of New Hampshire: Oikos, v. 26, Van Hook, R.I., Harris, W.F., and Henderson,p. 264-275. G.S., 1977, Cadmium, lead, and zinc dis-

Robertson, D.K., 1973, Ground water tributions and cyclingin a mixed deciduous

availability in southern New Jersey, report: forest: Ambio, v. 6, p. 281-286.

Elmer, NJ, C.W. Thornthwaite Ass. Lab. of Vuceta, Jasenka and Morgan, J.J., 1978, Chemi-Climatol. cal modelling of trace metals in fresh waters,

Role of complexation and adsorption: En-Schell, W.R., and Barnes, R.S., 1974, Lead andmercury in the aquatic environment of viron. Sci. Technol., v. 12, p. 1302-1309.

western Washington State: in Rubin, A..I., Wilding, LP., Smeck, N.E., and Drees, L.R.,editor, Aqueous-environmental chemistry 1977, Silica in soils, in Dixon, J.D., andof metals: Ann Arbor, MI., Ann Arbor Weed, S.B., editors, Minerals in soil en-Science, p. 129-166. vironments: Madison, W1, Soil Sci. Soc.

Schnitzer, Morris, and Skinner, S.I.M., 1%7, C _'- Am., p. 471-552.

gano-metalllic interactions in soils, 7, Williams, S.L., Aulenbach, D.B., and Clesceri,Stability constants of Pb, Ni, Co, Ca, and N.L, 1974, Sources and distribution of trace

Mg, fulvic acid complexes: Soil Sci., v. 103, metals in aquatic environments, in Rubin,p. 247-252. A.J., editor, Aqueous-environmental

Schwertmann, Udo, and Taylor, R.M., 1977, chemistry of metals: Ann Arbor, MI, AnnIron oxides, ht Dixon, J.B., and Weed, S.B., Arbor Science, p. 77-128.

editors, Minerals in soil environments: Zapeeza, O.S., 1984, Hydrogeologic frameworkMadison, WI.,SoilSci.Soc.Am., p. 145-175. of the New Jersey Coastal Plain: U.S.

Siccama, T.A., and Smith, W.H., 1978, Lead ac- Geological Survey Open-file Report 84-730,cumulation in a northern hardwood forest: 61p., 24 pl.

Environ. Sci. Technol., v. 12, p. 593- 594.

13

APPENDIX 1Trace metal levels in ground water

Trace metal levels in ground water, June 1978-March 1979 (after subtraction of mean values of blanks)*

Organic o,g/L Depth toDate of Well pH matter water table

collection no. (units) (A.U.) Pb C'u Ni Cd Fe Mn (cm)

6/22/78 1 4.7 0.01 86 23 10 13.6 132 124 202 5.4 0311 23 4 12 0.6 117 50 03 3.3 0395 21 4 4 13.6 447 33 96 3.2 0.57 28 2 5 4.6 699 13 0

mean 4.2 0.322 39.5 83 7.8 8.1 349 55 7.3

7/6/'/8 1 4.7 0.02 6 1 4 2.6 63 89 202 4.2 0.04 8 1 1 0.6 168 123 03 3.7 0.21 11 4 15 1.6 601 112 96 3.7 0.625 32 2 4 0.6 638 17 0

mean 4.1 0.224 143 2 6 1.4 367 88 7.3

7/19/78 1 3.9 0.025 55 2 5 2.6 72 96 322 4.3 0.02 12 3 2 0,6 62 79 2.53 3.7 0.34 19 2 4 <0.1 646 146 144 4.2 0.65 6 21 16 1.6 696 206 535 4.7 476 4.3 1.03 15 11 8 1.6 656 19 0

mean 4.2 0.413 21.4 7.8 7 1.3 426 109 25

8/3/78 1 4,2 0,02 18 3 2 2 98 51 12.52 3,1 0.035 20 2 < 1 < 0.1 164 56 5

3 2.8 0.17 34 6 < 1 < 0,1 617 87 154 4.9 0.165 8 4 9 0.2 745 143 535 4.6 1.1 59 25 19 0.1 808 73 526 3.6 1.4 39 9 6 0.2 782 19 0

mean 3.9 0.482 29.7 8.2 6 0,4 536 72 23

8/8/78 1 4.5 0.02 11 3 1 <0.1 522 52 7.52 4,5 0,04 13 5 2 <0.1 227 42 3.8

3 4,0 0,2 33 17 6 1.2 690 54 184 4.8 0.14 8 8 6 0.6 516 116 495 4.6 2.04 39 38 17 0.7 774 30 556 4.0 1.28 60 19 2 2.2 743 11 0

mean 4.4 0.62 273 15 5.7 0.8 579 51 22

9/13/78 1 4.2 0.01 5 8 2 3.3 162 53 2.52 4.4 0.01 8 5 2 0.7 452 42 2.5

3 3.7 0.01 14 24 6 0,6 1675 90 184 4.3 0,01 8 4 10 0.7 1649 187 505 4.9 23 19 7 0J 2715 10 456 3,7 59 14 4 7.5 2185 12 0

mean 4.2 0.01 19.5 12,3 5.2 2.2 1473 66 20

• Values< l:0were arbitrarilyset to 0.1andth(_;c< 0.l were setto 0.01instatisticalcalculatiomsandin plots,

15

Appendix 1. Trace metal levels in ground water* (cont.)

Organic Depth toDate of Well pH matter ttg/L water table

collection no. (units) (A.U.) Pb C'u Ni Cd Fe Mn (em)

9/29/78 1 4.7 0.01 3 10 1 5.3 60 73 102 4.5 0.02 1 2 7 2.1 50 44 53 3.8 0.17 12 53 4 1.3 619 111 204 4.9 0.06 3 1 7 2.0 689 141 535 3.7 0.19 4 49 8 1.9 728 6 88

mean 4.3 0.09 4.6 23 5.4 2.5 429 75 35.2

10/11/78 1 4.7 0.01 2 3 < 1 < 0.1 110 73 7.52 4.7 0.04 2 1 6 0.6 68 41 5

3 4.1 0.09 1 1 6 1.8 588 131 264 4.9 0.07 6 < 1 2 0.5 577 141 555 3.95 2 7 5 2.3 627 10 666 4.0 0.43 16 71 2 1.8 655 8 10

mean 4.4 0.128 4.8 13.9 3.5 1.2 436 67 28

10/25/78 1 4.7 0.01 3 1 72 0.2 79 76 12.52 4.5 0.02 2 1 13 < 0.1 47 46 6.43 4.0 0.025 3 < 1 1 0.3 302 92 244 4.6 0.025 3 < 1 < 1 0.3 200 113 586 3.9 0.32 4 12 9 2.4 388 17 15

mean 4.3 0.08 3.0 2.8 19 0.6 203 69 23

11/8/78 1 4.8 0.01 2 < 1 8 < 0.1 45 58 132 4.65 0.01 2 < 1 2 < 0.1 43 27 373 4.15 0.01 2 < 1 5 < 0.1 488 76 234 5.0 0.05 3 1 4 0.2 508 87 586 4.1 0.24 3 6 43 0.3 596 7 33

mean 4.5 0.064 2.4 1.5 12.4 0.1 336 51 33

12/1/78 1 4.8 0 2 1 10 0.2 59 64 02 4.6 0 2 2 39 < 0.1 93 32 83 3.9 0 2 1 3 0.1 422 67 204 4.7 0.025 3 2 6 0.2 134 76 606 3.7 0.05 3 2 6 0.1 421 19 0

mean 4.3 0.015 2.4 1.6 12.8 0.12 226 52 18

12/21/78 I 4.7 0.015 1 < 1 12 < 0.1 55 48 02 4.6 0.03 2 2 1 0.3 48 26 53 4.1 0.015 4 2 3 0.5 340 72 23

4 4.7 0.03 2 2 4 0.8 117 80 585 4.5 0.045 2 1 5 1.2 309 5 76

6 3.65 0.05 5 1 1 0.1 393 39 0mean 4.4 0.031 2.7 1.4 4.3 0.5 210 45 27

• Values < 1.0werearbitrarilyset to 0.1andthose < 0.1wereset to 0.01in statisticalcalculationsandinplots.

16

Appendix 1. Trace metal levels in ground water* (cont.)

Organic Depth toDate of Well pH matter ttg/L water table

collection no. (units) (A.U.) Pb Cu Ni Cd Fe Mn (cm)

1/10/79 1 4.7 0.01 < 1 < 1 5 0.1 53 46 02 4.5 0.035 1 < 1 1 0.1 44 92 03 4.1 0.045 1 1 3 0.3 395 93 184 4.5 535 4.2 0.02 1 1 3 0.2 243 5

mean 4.4 0.028 0.8 1.0 3 0.18 184 59 18

2/10/79 1 4.7 0 < 1 < 1 15 < 0.1 130 60 02 4.6 0.02 <1 1 2 <0.1 93 47 03 4.3 0.07 6 3 2 0.4 550 80 134 4.2 0.1 1 5 3 0.4 345 93 455 4.3 0.03 < 1 < 1 4 0.2 508 8 48

mean 4.4 0.044 1.5 1.8 5.2 0.2 325 58 21

3/1F/9 1 4.9 0 <1 <1 <1 <0.1 47 59 02 4.7 0.02 1 < 1 < 1 0_3 47 55 03 4.6 0.02 5 < 1 1 0.3 283 77 84 4.1 0.18 2 2 < 1 0.3 283 59 355 4.2 0.02 3 1 1 < 0.1 354 5 186 3.8 0.13 5 8 2 0.1 579 18 0

mean 4.4 0.062 2.7 1.9 0.7 0.2 266 46 10

• Values < 1.0 were arbitrarily set to 0.1 and thccse < 0.1 we_ set to 0.01 in statistical calculations and in plots.

17

APPENDIX 2Trace metal levds in precipitation

Trace metal levels in precipitation (dry fallout plus rain or snow) from May 1978 to March 1979"

Date of Sample pH p.g/Lcollection number (units) Pb Cu Ni Cd Fe Mn

6/22/78 6 3.75 28 8 12 0.1 93 226/22 7 3.7 13 9 3 <0.1 105 7

7/6 8 4.5 7 6 6 <0.1 46 57/19 9 3.4 11 8 4 <0.1 76 14

8/3 10 3.6 26 11 1 <0.1 82 128/9 11 3.6 9 8 1 < 0.1 21 58/9 12 3.6 10 7 2 <0.1 17 1

8/22 13 3.8 20 1 2 < 0.1 19 18/22 14 3.7 20 1 12 1.1 13 1

9/1 15 3.7 19 2 14 <0.1 28 19/22 16 3.6 38 4 6 0.3 111 1069/22 17 3.3 49 9 46 0.5 158 239/29 18 3.3 118 4 14 0.3 107 1310/6 19 3.5 23 1 2 0.1 37 14

10/25 20 4.0 47 8 6 0.2 99 83

10/30 21 3.9 27 4 5 0.3 101 112

11/19 22 4.1 16 1 5 < 0.1 37 2011/19 23 4.05 29 3 22 <0.1 70 21

12/1 24 4.1 13 1 5 <0.1 33 6

12/21 25 4.1 7 1 4 <0.1 8 312/21 26 4.45 7 2 4 <0.1 6 1

1/5/79 27 4.1 4 8 6 < 0.1 12 11/5 28 4.3 7 1 2 < 0.1 8 41/5 29 4.2 7 1 3 0.8 12 871/9 30 4.0 11 1 4 2.5 15 1

1i23 31 4.0 6 1 1 < 0.1 18 182/10 32 4.1 61 2 1 5.8 155 202/26 33 3.8 12 1 1 < 0.1 23 53/19 34 4.2 12 1 1 1.3 22 5

* Data adaptedfromSwanson,1979;valuesaftersubtractionof meanvaluesof blanks

Values<0.1werearbitrarilyset to 0.01instatisticalcalculationsandinplots.

Forthosedateswithmorethanone sample,me.anconcentrationswereusedin the plots.

19

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