Air & Waste

ISSN: 1073-161X (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/uawm19

Bioaccumulation of Mercury by Sphagnum Moss

Near a Municipal Solid Waste Incinerator

Anthony Carpi , Leonard H. Weinstein & Daryl W. Ditz

To cite this article: Anthony Carpi , Leonard H. Weinstein & Daryl W. Ditz (1994) Bioaccumulation
of Mercury by Sphagnum Moss Near a Municipal Solid Waste Incinerator, Air & Waste, 44:5,
669-672, DOI: 10.1080/1073161X.1994.10467270

To link to this article: http://dx.doi.org/10.1080/1073161X.1994.10467270

Published online: 05 Mar 2012.

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 FEATURE

Bioaccumulation of Mercury by Sphagnum

Moss Near a Municipal Solid Waste
Incinerator
Anthony Carpi and Leonard H. Weinstein Daryl W. Ditz
Boyce Thompson Institute for Plant Research World Resources Institute
Cornell University Washington, DC
Ithaca, New York

Sphagnum moss {Sphagnum spp.) and Italian ryegrass {Lolium multiflorum Lam.) were used as biological monitors of
atmospheric mercury around a municipal solid waste incinerator in rural New Jersey. Moss and grass samples were exposed
according to standardized techniques at sixteen sites within 5 km of the incinerator. One remote site was monitored to establish
background field accumulation. Duplicate and control monitors were used for quality assurance. In all cases, mercury concentrations
in moss exceeded those in grass. Mercury accumulation by moss exhibited a spatial pattern consistent with a local source of
pollution, considering wind and precipitation. Total mercury in moss exposed at sites within 1.7 km of the incinerator averaged 206
ppb while samples exposed at greater distances from the facility averaged 126 ppb.

Estimates of the health risks from the incineration of municipal
solid waste (MSW) are based on emissions data from infrequent
stack tests together with complex models of pollutant transport
and fate.' However, few efforts have been made to validate these
extrapolations with measurements of actual exposure. The princi-
pal obstacle to actual field validation stems from the small
incremental impact these sources have on ambient pollutant
concentrations. In some cases, the presence of industrial, utility,
and transportation sources confounds efforts at source attribution.
One promising approach for validating an important part of total
exposure employs biological monitors. In this field experiment,
standardized moss and grass samples were used as accumulators
of airborne mercury. These results shed light on the importance of
local variations of mercury on biological media.
Biological monitoring using plants as receptors offers two
important advantages over conventional ambient air monitoring.
Since no instrumentation or electrical power is required, many
more sites can be established, thereby improving spatial resolu-
tion at relatively low cost. Second, pollutant accumulation by
plants provides a direct, though partial, measure of food chain
contamination. For most organic pollutants and heavy metals
emitted by MSW incinerators, human exposure via consumption
of vegetables, fish, dairy products and meat dominates exposure
Implications
The Clean Air Act Amendments of 1990 and other recent regulatory
actions highlight the importance of mercury from municipal solid waste
(MSW) incinerators. In this field experiment, moss samplers deployed
around a modern MSW incinerator showed elevated concentrations of
mercury over samples exposed at a distance from the facility. These
results suggest that a local source of airborne mercury affects the
accumulation of the metal in biological media. The significance of local
pollutant accumulation, demonstrated by this research, is an important
factor to consider in human and ecological health risk assessment.
by inhalation.2 For mercury, these indirect ingestion pathways are
estimated to account for between 81.9 and 99.8 percent of the
overall dose.3 A few environmental monitoring projects have
collected samples near MSW incinerators.46 However, small
numbers of samples have led to inconclusive results.
Mercury is a pollutant of particular importance to human
health risk studies because it is a mutagen and a teratogen, as well
as a neurological and behavioral toxicant.7 The majority of mer-
cury present in MSW is volatilized during combustion.8 Although
the exact speciation of mercury is unknown, it is believed that
mercury would exit the stack primarily as elemental mercury
(Hg), HgCl2 and other inorganic forms.9 Pending regulatory
actions highlight the importance of mercury from MSW incinera-
tors. The Clean Air Act Amendments of 1990 require EPA to
establish limits on mercury emissions from MSW incineration.10
In 1991, New Jersey created a special Task Force to develop new
mercury standards for MSW incinerators.11
During the summer of 1991, we established a biological
monitoring network near the Warren County Resource Recovery
Facility (WCRRF), a MSW incinerator located near the junction
of Routes 46 and 31 in Oxford Township in rural northwestern
New Jersey. The WCRRF burns approximately 400 tons of MSW
per day in its two mass-burn combustion units. It is equipped with
a spray dryer for acid gas control and fabric filters for capturing
particulates. The WCRRF was required to conduct additional
stack tests due to earlier violations of its permit limits for mercury.
In addition, the New Jersey Department of Environmental Protec-
tion and Energy was supporting an intensive ambient air monitor-
ing and rainwater sampling project to assess mercury concentra-
tions in the area.12
The incinerator is situated in complex terrain; a range of hills
dominates the landscape to the north and south of the facility. A
large portion of the land surrounding the WCRRF is agricultural.
Copyright 1994 - Air & Waste Management Association

AIR & WASTE Vol. 44 May 1994 669

 FEATURE

Although industrial development in the area is light, there is a ducibility. These replicate analyses varied by less than 10 percent
coal/oil-burning electric generating plant in Martin's Creek, Penn- of the total mercury concentration in the samples. Results from
sylvania (8 km west-southwest of the WCRRF). The combustion chemical analysis of the samples are included in Table I.
of coal is a significant source of airborne mercury.13 Sphagnum moss proved to be a good accumulator of mercury.
The concentrations of mercury in the moss samples are repre-
Experimental Design sented by the height of the bars imposed on the site map in Figure
Our objective was to determine if spatial patterns of mercury 1. The concentration of mercury at the Delaware Water Gap site
accumulation could be detected in vegetation samples and to consider Table I: Site locations and mercury concentrations in moss and grass. (All
the potential significance of indirect exposures to mercury. Sixteen concentrations in ppb on dry weight basis).
biological monitoring stations (sites FS1-FS16) were located within
a 5 km radius of the WCRRF. In addition to the sixteen proximal sites, UTM (km) UTM (km) Undried Oven- Undried Oven-
one remote station (site FS17) was located near the Delaware Water Site North East Moss Dried Grass Dries
Gap National Recreation Area, approximately 20 km north of the Moss Grass
incinerator and 5 km from any major industrial source of air pollution. FS1 4518,9 498.9 188,9 179.9 39.1 29.9
Because of the distance from the incinerator and other air pollution
sources, the remote site was expected to provide a measure of FS2 4518.7 500,2 195.4 142,7 73 31.4
background field exposure from regional and long-range sources. (138,7)t
Additional moss and grass controls were used to establish baseline 173tt 194 65 51
(59) (52)
contamination of the biological samples and to quantify procedural
and processing contamination. FS3 4519.3 497,7 230.6 137,3
Because pollutant accumulation varies even between plants
exposed at the same location, site duplicates were used in this FS4 4517.1 498.8 193.6 183.8
(204.8)
study to help quantify the inherent variability of the samples.
Duplicate plant monitors exposed to the same conditions were FS5 4517.6 500.2 211.1 148.6 32.5 38.5
used at 10 field sites to measure variability in accumulation of the 253.5 191.3 44.9 32.1
biomonitoring systems.
FS6 4518.3 500,6 107.8 96.2 22.6 37.4
Each of the 17 monitoring stations held two species of plants, (89.9) (32.6)
(29.1)
sphagnum moss (Sphagnum spp.) and Italian ryegrass (Lolium
multiflorum L.). Sphagnum moss is a well known accumulator of FS7 4520.5 499,0 122.1 95.6 42.6 45,2
mercury.l4 Grass has been used extensively as a biomonitor and is 117.9 131.3
eaten by cattle, thus providing a link to meat and dairy accumula-
tion of mercury.1516 Moss was suspended in fine mesh bags in a FS8 4517.9 496.9 105.1 87.1
139,7 72,7
slight modification of published methods.1718 A self-watering
grass culture was modified from the design first proposed by FS10 4518.9 501.8 132.6 133.9
Scholl to standardize growth conditions.19 In this system, a fiber- 120.3 106.5
glass wick extending from the soil to a water reservoir supplies a (108,3)
constant and even flow of water to the plant. In accordance with FS11 4517.2 501.7 132 815
a strict protocol, the soil mixture, water and age of plants were all
standardized, thus reducing the number of factors affecting pollut- FS12 4521.9 498.2 141.5 84.1
ant accumulation. This design uses common materials, requires little (152)
maintenance, and allows easy replacement of plants after exposure.
FS13 4520.1 495.5 102,6 99 18.6 22,8
Strict sample preparation, collection and storage procedures (115) (115) (24)
and analytical protocols were established to minimize mercury (109)
contamination to the samples and insure the quality of the re-
sults.20 Field sampling was conducted from June 11 through FS14 4520.8 502.3 122.9 123,2
September 17, 1991. The field location was visited every two (138.2)
122.5 103.5
weeks to harvest and replace the biomonitors. After harvest,
samples were prepared and stored in polyethylene bags at -20C FS15 4517.1 494.8 182.4 113.6 30.4 33.2
pending chemical analysis. A set of samples exposed in the field (25.5)
from July 9 through July 23, 1991 was analyzed for mercury by
cold vapor atomic absorption spectroscopy.2122 Each sample was FS16 4519.8 503.8 132.4 99.6 54 39.1
(130.2) (115) (52.3) (52)
split into two. One portion was digested and analyzed as received. (111.2)
The other fraction was oven-dried at 105C for 24 hours prior to 129 110.1 75.6 53.8
digestion and analysis. (116.9) (117.9)

Results and Discussion FS17 4539.0 497.5 148.6 55.7 46.7 12.8
(Remote) (134) (13.5)
Samples of a National Institute of Standards and Technology 127.2 46.9 28.5 13
(NIST) vegetation reference material (No. 1547, dried peach (12.1)
leaves) were included in the analyses to determine the accuracy
and sensitivity of the laboratory analysis. The concentrations of WCRRF 4518.6 498.9
mercury reported by the laboratory in three samples of the refer-
Control 58 60.4 54 33
ence material were 33.6,31.8 and 31.4 ppb, these values were well 39 48 40.1 46.8
within the 95 percent confidence interval (31 7 ppb) certified by 54.3 48,6
NIST.
A number of moss samples were analyzed in replicate by the t Replicate laboratory analyses shown in parenthesis,
laboratory to provide an estimate of analytical quality and repro- f t Site duplicates separated by rows.

670 May 1994 Vol. 44 AIR & WASTE

and in the control samples are shown in the left margin. Co-located
duplicate samples are shown as side-by-side concentration bars.
The difference in mercury concentration between site duplicates ranged
from 4 to 53 ppb. In contrast, the replicate laboratory analyses account for
about half of this variability, ranging from 2 to 18 ppb. Thus natural
biological variation and analytical error were found to contribute equally
to the difference between duplicate plant samples. This variation between
site duplicates is small compared with the variation between samples
exposed at different sites.
Higher concentrations of mercury occurred at sites closest to
the WCRRF (Figure 1). An analysis of variance (ANOVA) was
conducted on the site duplicates to determine if a significant
difference existed between the samples above the duplicate vari-
ability. The difference was highly significant (p-value < 0.01),
indicating that mercury accumulation is affected by a local source
and not simply by natural accumulation differences between
different moss samples.
Confidence intervals of mercury concentration at each dupli-
cated site were computed based on the pooled standard deviation
calculated in the ANOVA. In the undried moss samples, the
mercury concentration in every sample exposed in the field was
significantly higher than the mercury concentration in the control
samples. In addition, the concentrations of mercury at sites FS2
and FS5, the two duplicated sites closest to the WCRRF, were
greater than at any other monitoring site.
The ANOVA revealed that higher concentrations of mercury
are found close to the incinerator. With that established, the spatial
pattern of mercury accumulation was compared to wind and
precipitation because of the role these meteorological events play
in the movement of pollutants in the atmosphere. The wind rose
presented in Figure 1 was constructed using data from the nearest
National Weather Service station at Allentown, Pennsylvania, 38 km
southwest of Oxford, New Jersey.23 This wind rose was calculated for
the period July 9, 12:00 p.m. to July 23, 12:00 p.m. by plotting the
relative frequency of the direction toward which the wind was
blowing (observed at 3-hr intervals) as the length of a slice of pie. The
higher frequency of wind to the north and east of the WCRRF
corresponds well with high concentrations of mercury in the moss
monitors. The complex terrain of the region however, introduces
considerable uncertainty regarding local conditions.
In addition to the high concentrations of mercury correspond-
ing with the prevailing wind directions, a high concentration was
also found at site FS3, a station that was upwind of the incinerator
during most of the exposure period. In other research, rainwater
collected around the WCRRF contained higher concentrations of
mercury immediately downwind of the incinerator.24 This sug-
gested that mercury was scavenged by precipitation and deposited
near the facility. During the two week exposure period, two strong
rainfall events were recorded at the Allentown station. It is
FS17
Remote
Figure 1. Mercury concentrations in undried moss samples.
interesting, although not conclusive, that on July 13, as 3.5 cm of
rain fell, the wind at Allentown was to the northwest. Although
precipitation is often localized, this rain event was verified by
measurements taken within 6 km of the WCRRF. 25
Mercury uptake by moss was also examined by plotting con-
centration as a function of distance from the incinerator (Figure 2).
The concentrations of mercury at the remote site and in the control
moss samples are displayed in the right-hand margin of the graph;
duplicates are plotted with a line connecting the two values. Figure
2 suggests three levels of mercury accumulation. The concentra-
tions of mercury in the control moss range from 40 to 60 ppb. At
a distance of less than 1.7 km mercury concentrations fall between
180 and 250 ppb. And, with one exception, mercury concentra-
tions at all other distances, including the remote site, fall between
100 and 150 ppb. The high concentration of approximately 190
ppb was recorded at site FS15, roughly 4.5 km west-southwest of
the WCRRF. The concentration of mercury at this site is much
higher than other distant stations. However, this site is the closest
sampling station to the coal/oil-burning power plant in Martin's
Creek, Pennsylvania. Site FS15 sits on the crest of a hill roughly
halfway between the WCRRF and the power plant.
Results of the mercury analysis on samples after oven-drying
at 105C for 24 hours revealed an interesting finding. Because
mercury is volatile, and volatility depends on complexation state,
a comparison of the concentration of mercury in the samples
before and after oven-drying may provide an insight into specia-
tion. Certain species, especially Hg, would be lost during oven-
drying and only less volatile species such as the inorganic com-
plexes of mercury would remain in the samples. The concentra-
tion of mercury remaining in the moss samples after oven-drying
are plotted versus distance from the WCRRF in Figure 3.
In general, mercury concentrations were lower after oven-
drying, consistent with the expected loss on heating. Yet high
concentrations of mercury remained in samples collected close to
the WCRRF. The sharp differences evident in Figure 2 were not as
dramatic with the oven-dried samples. Still, mercury concentrations
within 1.7 km of the incinerator were greater than other sites.
Although the concentrations of mercury in the undried samples
from the remote site were significantly greater than the controls,
after drying these samples appear to have lost all of the mercury
accumulated in the field. Mercury in the undried samples at the
remote site indicated significant contributions to background
mercury levels in the region. If the accumulation of mercury at the
remote site was indicative of distant mercury sources, the physical
properties of the accumulated metal should be similar at the sites
near the WCRRF. But, the concentration of mercury in the overi-
Distance from the WCRRF (km)
Figure 2. Mercury concentrations in undried sphagnum moss.
AIR & WASTE Vol. 44 May 1994 671
 FEATURE
dried moss from the remote site was nearly equal to the concentra-
tion in the control sample. The species of mercury accumulated at
the remote site were more volatile than those accumulated near the
incinerator. This suggested the presence of a different source of
mercury near the remote location.
Although both moss and grass samples were used in the study,
results from the Italian ryegrass samples were inconclusive. The
mercury concentrations detected in the ryegrass samples were
considerably lower than in the moss samples. The mercury found
in the grass samples did not exhibit any patterns of accumulation
consistent with a local point source of pollution. Several grass
samples exposed in the field had lower mercury concentrations
than the controls.
Mercury accumulation by moss may indicate an increase in the
metal in other plants directly or indirectly consumed by humans.
If the accumulation of mercury seen with sphagnum moss is
indicative of mercury accumulation in vegetables and other pro-
duce consumed by humans, the observed increase of mercury in
moss may denote a significant pathway of human exposure to
mercury. This work underscores the need for additional research
to quantify mercury accumulation in vegetables and other human
foodstuffs grown near MSW incinerators and other sources of
airborne pollutants.
300
200
a,
I
a
a Pollut. 6:1 (1974).
1 2 3 4 5 atmospheric deposition," JAPCA 31:668 (1981).
Distance from the WCRRF (km)
Figure 3. Mercury concentrations in dried sphagnum moss.
Conclusions
Mercury accumulation by sphagnum moss was elevated near a
modern municipal solid waste incinerator. Moss bags exposed at
sites within 1.7 km of the facility accumulated an average of 63
percent more mercury than moss exposed at more distant sites.
The spatial pattern of mercury accumulation by moss was consis-
tent with local wind and precipitation events. After oven-drying,
all moss samples lost mercury. However, the spatial pattern was
still evident. Differential mercury losses after oven-drying may
reflect the mix of mercury species accumulated by the samples.
This research demonstrates the practical value of biological moni-
toring as a tool for assessing spatial patterns of pollutant exposure.
The increased accumulation of mercury in moss near the MSW
incinerator highlights the importance of food-chain exposure
pathways in health risk assessments.
Acknowledgments
Support for this research was provided by the Boyce Thompson Institute
for Plant Research, the Waste Management Institute at Cornell University and
the New Jersey Department of Environmental Protection and Energy. Fund-
ing was also provided by an ALCOA Foundation grant and the National
672 May 1994 Vol. 44 AIR & WASTE
Institute of Environmental Health Sciences grant #ES07O52 for graduate
education. Special thanks to Andrea Sultana and Steven Krivanek for their
technical assistance.
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About the Authors
A. Carpi, M.S., is a doctoral fellow in the field of Environmental Toxicology
at Cornell University working at the Boyce Thompson Institute for Plant
Research, Tower Rd., Ithaca, NY 14853. D.W. Ditz, Ph.D., is an associate in the
Program in Technology and the Environment at the World Resources Institute,
1709 New York Ave.,NW, Washington, DC 20006. LH.Weinstein, Ph.D., is the
William Boyce Thompson scientist at the Boyce Thompson Institute for Plant
Research, Tower Rd., Ithaca, NY 14853. This manuscript was submitted for
peer review on November 5, 19.93. The revised manuscript was received on
January 31,1994.