AND HEAVY METAL CONCENTRATIONS IN ARIZONA OBSERVED IN NATURAL WETLAND By

MICRONUTRIENT AND HEAVY METAL CONCENTRATIONS
OBSERVED IN NATURAL WETLAND MACROPHYTES IN ARIZONA
By
Laska Rohovit
Thesis Submitted to the Faculty of the
DEPARTMENT OF SOIL, WATER AND ENVIRONMENTAL SCIENCE
In Partial Fulfillment of the Requirements
For the Degree of
MASTER OF SCIENCE
In the Graduate College
THE UNIVERSITY OF ARIZONA
1999
2
STATEMENT OF AUTHOR
This thesis has been submitted in partial fulfillment of requirements for an
advanced degree at the University of Arizona and is deposited in the University Library
to be made available to borrowers under rules of the Library.
Brief quotations from this thesis are allowable without special permission,
provided that accurate acknowledgment of source is made. Requests for permission for
extended quotation from or reproduction of this manuscript in whole or part may be
granted by the head of the major department or the Dean of the Graduate College when in
his or her judgment the proposed use of the material is in the interests of scholarship. In
all other instances, however, permission must be obtained from the author.
Signed:
APPROVAL BY THESIS DIRECTOR
This thesis has been approved on the date shown below:
3
ACKNOWLEDGMENTS
I would like to sincerely thank Dr. Janick Artiola in the Department of Soil, Water
and Environmental Sciences, Dr. Martin Karpiscak in the Office of Arid Lands Studies,
and Dr. Ed Glenn in the Department of Soil Water and Environmental Sciences for their
guidance throughout this research. I would also like to thank Jeff Conn for his assistance
in both the field and laboratory.
I am grateful to Dr. Chris Amrhein and Jim Strong at the University of California,
Riverside for granting me use of their facilities and instrumentation.
4
TABLE OF CONTENTS
Page
LIST OF FIGURES 6
LIST OF TABLES 7
ABSTRACT 9
CHAPTER 1: BACKGROUND INFORMATION 10
Factors Necessitating Research 10
Constructed Wetland Treatment Systems 10
Environmental Factors Affecting Elemental Accumulation 14
Physiological Factors Affecting Elemental Accumulation 17
Literature Review 18
CHAPTER 2: RESEARCH OVERVIEW 28
Site Selection 28
Plant Species Selection 33
Elemental Analysis 33
Data Analysis 35
CHAPTER 3: METHODS AND TECHNIQUES 38
Sample Collection 38
Sample Preparation 39
Sample Analysis 42
CHAPTER 4: RESULTS AND DISCUSSION 44
Aluminum 44
Arsenic 48
Cadmium 52
5
TABLE OF CONTENTS — Continued
Page
Chromium 54
Cobalt 57
Copper 59
Iron 63
Lead 67
Manganese 71
Nickel 75
Selenium 77
Zinc 80
CHAPTER 5: CONCLUSIONS 84
APPENDIX A: EMPIRE CIENEGA 89
APPENDIX B: CANELO HILLS CIENEGA 91
APPENDIX C: PATAGONIA-SONOITA CREEK PRESERVE 93
APPENDIX D: ST. DAVID CIENEGA 95
APPENDIX E: AGUA CALIENTE PARK 97
APPENDIX F: COOK'S LAKE 99
APPENDIX G: BINGHAM CIENEGA 101
APPENDIX H: COMPLETE PLANT DATA BY STUDY SITE 103
REFERENCES 107
6
LIST OF FIGURES
Page
Figure 1: Life forms of aquatic macrophytes commonly used in constructed
wetland systems 13
Figure 2: Selected wetland locations throughout Southern Arizona 30
Figure 3: Mean copper concentrations in the tissues of wetland macrophytes 62
Figure 4: Mean iron concentrations in the tissues of wetland macrophytes 66
Figure 5: Mean lead concentrations in the tissues of wetland macrophytes 70
Figure 6: Mean manganese concentrations in the tissues of wetland macrophytes 74
Figure 7: Mean zinc concentrations in the tissues of wetland macrophytes 83
7
LIST OF TABLES
Page
Table 1: Major chemical forms of trace elements in soil solutions and aqueous
environments 15
Table 2: Summary of trace metal concentrations in freshwater plants from
uncontaminated environments 19
Table 3: Approximate concentrations of trace elements in mature leaf tissue
generalized for various species 20
Table 4: Trace element content of a "reference plant" 22
Table 5: Selected chemical parameters in plant tissue samples from potable
and effluent-fed constructed wetland systems 24
Table 6: Selected chemical parameters in plant leaf, root and flower samples
from potable and effluent-fed constructed wetland systems 26
Table 7: Elemental concentrations in emergent, submerged and floating-leaved
life forms of aquatic and wetland plants 27
Table 8: Selected sites, wetland types and ownership 29
Table 9: System of categories for determining the occurrence of wetland plants 34
Table 10: Selected plant species and their wetland categories 34
Table 11: Selected elements and their biological classifications and functions 36
Table 12: Sampling schedule 38
Table 13: Plant tissue samples collected at each of the seven sites 40
Table 14: Summary of nutrient and heavy metal concentrations observed in the
tissues of selected naturally occurring wetland macrophytes in Arizona 45
Table 15: Aluminum concentrations observed in naturally occurring wetland
macrophytes 46
Table 16: Nutrient and heavy metal concentrations observed in water samples
from natural wetland sites in Arizona 47
8
LIST OF TABLES - Continued
Page
Table 17: Nutrient and heavy metal concentrations observed in soil samples
from natural wetland sites in Arizona 49
Table 18: Arsenic concentrations observed in naturally occurring wetland
macrophytes 50
Table 19: Cadmium concentrations observed in naturally occurring wetland
macrophytes 53
Table 20: Chromium concentrations observed in naturally occurring wetland
macrophytes 55
Table 21: Cobalt concentrations observed in naturally occurring wetland
macrophytes 58
Table 22: Copper concentrations observed in naturally occurring wetland
macrophytes 60
Table 23: Iron concentrations observed in naturally occurring wetland
macrophytes 64
Table 24: Lead concentrations observed in naturally occurring wetland
macrophytes 68
Table 25: Manganese concentrations observed in naturally occurring wetland
macrophytes 72
Table 26: Nickel concentrations observed in naturally occurring wetland
macrophytes 76
Table 27: Selenium concentrations observed in naturally occurring wetland
macrophytes 78
Table 28: Zinc concentrations observed in naturally occurring wetland
macrophytes Table 29: Summary of nutrient and heavy metal concentrations in the tissues
of macrophytes reported for various environments 81
87
9
ABSTRACT
The use of macrophytes for the treatment of wastewater in constructed wetlands
has caused concern over the possible concentration of elements within plant tissues. To
better understand the potential of constructed wetland systems for adverse impacts,
research was conducted to determine ranges at which micronutrients and heavy metals
naturally exist in the root, shoot and leaf tissues of wetland plants in southern Arizona.
Lemna sp., Anemopsis californica and Scirpus americanus concentrated the highest levels
of micronutrients and heavy metals. Leaves of tree and shrub species usually had the
lowest micronutrient and heavy metal concentrations of the plants analyzed in this study.
Root tissues generally had higher concentrations of most elements, although elevated
concentrations of micronutrients and heavy metals were found in the shoots of Typha
domingensis and the leaf tissues of Anemopsis californica.
10
CHAPTER 1: BACKGROUND INFORMATION
Factors Necessitating Research
Constructed wetland systems have proven to be a cost-effective, viable alternative to
traditional wastewater treatment and an environmentally sound method for polishing
wastewater (Karpiscak et al., 1996; Cole, 1998). However, the rapid rate at which
wetlands are being constructed, with over 500 operational in Europe and 600 in North
America, has caused some concern over the impact of such systems (Debusk et al., 1996;
Cole, 1998). Many studies have demonstrated that concentrations of essential and nonessential elements are substantially higher in plant tissues than in sediments and the
surrounding aquatic environment (Outridge and Noller, 1991; Albers and Camardese,
1993a). Bioconcentration of the nutrients and heavy metals present in wastewater may
pose a risk to animal inhabitants of constructed wetlands as well as to human health.
Elemental concentration may also lead to the production of toxic plant biomass, which
should be handled in an appropriate manner upon wetland harvesting. An inadequate
understanding of the degree to which nutrients and heavy metals are concentrated in the
tissues of macrophytes within constructed wetland treatment systems has prompted this
research.
Constructed Wetland Treatment Systems
Ecosystems dominated by aquatic macrophytes are known to be some of the most
productive environments in the world (Brix and Schierup, 1989). With this in mind,
researchers have exploited the ability of macrophytes to acquire and assimilate nutrients
11
by the construction of wetlands for agricultural and municipal wastewater treatment. In
addition, macrophytes have been found to remove heavy metals by uptake and
immobilization within plant tissues, making them suitable for mine drainage and
industrial wastewater treatment (Gupta et al., 1994; Dushenko et al., 1995; GoodrichMahoney, 1996; Knight et al., 1999). Constructed wetland systems have been
investigated internationally for several decades, and their capacity to reduce levels of
pathogens, suspended solids, biochemical oxygen demand (BOD), nutrients and heavy
metals has been documented (Reed et al., 1988; Martin and Fernandez, 1992; Karpiscak
et al., 1996, Knight et al., 1999).
Constructed wetland systems rely on the sun and gravity for energy, and the soil,
plant and microorganism matrix to retain and degrade the contaminants found in
wastewater (Goodrich-Mahoney, 1996). Wetland vegetation acts to slow effluent flow,
allowing for the sedimentation of suspended particles (Juwarkar et al., 1995), while
assimilating nutrients and heavy metals from the sediments and ambient water into new
plant biomass (Brix and Schierup, 1989). Perhaps more importantly, wetland vegetation
acts as a substrate for large and diverse microbial populations. Translocation of oxygen
through the plant body creates an aerobic microenvironment at the rhizosphere, where
microorganisms degrade nutrient, organic and metal pollutants and mediate chemical
reactions (Knight et al., 1995; Goodrich-Mahoney, 1996). The physical, biological and
chemical reactions that occur in wetlands allow contaminants of differing characteristics
to be physically removed, adsorbed to surfaces, or chemically transformed and stored
within the wetland matrix (Gersberg et al., 1986; Goodrich-Mahoney, 1996).
12
A variety of vegetation has been used in wetland systems designed for wastewater
treatment, including large trees and emergent, submergent and floating-leaved aquatic
macrophytes. Brix and Schierup (1989) illustrated the major life forms of aquatic
macrophytes commonly used in constructed wetlands (Figure 1). Large trees such as
cottonwood, ash and willow are often found in natural wetlands, but their use in
constructed wetlands is sparse, as their function in the treatment system has not yet been
defined. Emergent aquatic macrophytes dominate in engineered systems because of their
extensive root systems, with Typha (cattail), Scirpus (bulrush) and Phragmites (common
reed) being the most commonly propagated species (Havens et al., 1997). Typha and
Scirpus, or a combination of the two, are the most prevalent wetland vegetation types in
the United States, with Phragmites dominating in European systems (Cooper and Green,
1995; Cole, 1998). Floating-leaved aquatic macrophytes such as Lemna (duckweed) and
Eichhornia (hyacinth) are often used in constructed wetlands because they have rapid
growth rates and can be easily harvested (Karpiscak et al., 1994; Sharma and Gaur,
1995). Submergent aquatic macrophytes have not been extensively used for wastewater
treatment (Karpiscak, 1999). In choosing vegetation for a constructed wetland system, it
is important to select species that are efficient at nutrient and contaminant removal, and
those that are the least sensitive to phytotoxicity.
Artificial wetlands are constructed with a great degree of control, experimental
treatment facilities may vary the substrate composition, vegetation type, flow patterns,
wastewater type and loading rates to obtain effluents having advanced secondary
treatment quality (Brix and Schierup, 1989). In addition to wastewater treatment,
13
I. Emergent Aquatic Macrophytes
Scirpus
(bulrush)
Typha
(cattail)
II. Floating-leaved Aquatic Macrophytes
-1-117rtrir
. 1 •
•
•••,• • '.'
Eichhornia
(hyacinth)
Nymphaea
(water lily)
. ' • • •
•
. ,
.
,• • • • •'•
•
•
Lemna
(duckweed)
III. Submerged Aquatic Macrophytes
Potamogeton
(pondweed)
Littorella
(shoreweed)
Figure 1: Life forms of aquatic macrophytes commonly used in
constructed wetland systems (Brix and Schierup, 1989)
14
constructed wetlands are thought to improve the landscape and provide habitats for a
variety of wildlife, while treated wastewater can be used to irrigate parks and golf courses
(Greenway and Simpson, 1996). As an inexpensive, low-maintenance technology,
constructed wetland systems are increasingly being considered a treatment option for
various wastewater problems.
Environmental Factors Affecting Elemental Accumulation
The most critical environmental factors controlling elemental uptake by macrophytes
are concentration and chemical speciation within sediments and the water column (Van
der Werff, 1981; Alloway, 1995). Elements are present in a wide range of chemical
forms in sediments and the aqueous environment, in both dissolved and particulate
phases (Morrison, 1990). Dissolved chemical species include hydrated ions and
inorganic and organic complexes, while particulate phases include heterogeneous colloids
and organometallic compounds (Langmuir, 1997). Major chemical forms of trace
elements in soil solutions and aqueous environments are listed in Table 1. Elements
dissolved in the form of free ion species are the most readily taken up by plants, although
weak-ion and lipid-soluble complexes can also be highly bioavailable (Jones et al., 1991;
Phillips, 1995).
In aquatic environments, many variables determine chemical speciation and
solubility, including pH, redox potential and the formation of insoluble metal complexes.
Concentrations of dissolved elemental species are inversely related to pH, especially for
the elements aluminum, cadmium, iron, manganese, lead and zinc (Albers and
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Camardese, 1993a,b). A decrease in pH effectively increases the concentration of free
ions, and thus greater metal absorption by plants. Aquatic systems that are subject to acid
deposition, and those which are poorly buffered are the most sensitive to the effects of pH
on metal speciation (Van der Werff, 1981).
Redox state determines the chemical form of an element, and thus its behavior in the
environment. Hydric soils and a high organic content, both characteristic of wetlands,
limit oxygen availability and push a system towards reduced conditions (Langmuir,
1997). Reduction occurs by both chemical oxidation and biochemical oxygen depletion
from microbial respiration. Nitrate is the first soil component reduced (NO3 - -->NO2")
followed closely by manganic manganese (Mn 4+ --->Mn2+) (Vymazal, 1995). Reductions
of oxygen, nitrate and manganese may occur simultaneously, although subsequent
reductions of iron, sulfate and carbon dioxide will not occur unless the preceding element
has been completely reduced (Vymazal, 1995). Ferric iron is reduced to ferrous iron
(Fe3± —>Fe2+) the predominant form in wetlands, which is the most soluble form and
readily available to plants. In its reduced form, iron causes a bluish-gray coloration of
soils, indicative of low redox potential (Vymazal, 1995). After iron reduction, sulfate is
reduced to sulfide (SO4 2- ->S 2-) a process that gives waterlogged soils a characteristic
rotten-egg smell. Sulfate acts as a terminal electron acceptor for many metals, including
cadmium, chromium, cobalt, copper, lead, mercury, nickel and zinc, forming insoluble
metal-sulfide compounds (Chino, 1981; Vymazal, 1995; DeLaune et al., 1998). Carbon
dioxide reduction to methane (CO2--->CH4) also occurs under reduced conditions, usually
when sulfate is present at low concentrations (Vymazal, 1995). Like iron, arsenic and
17
manganese become more bioavailable under reduced conditions, due to redox species
changes (Chino, 1981). Depth of the aquatic macrophyte root system is an important
factor affecting elemental accumulation, as root tissues may inhabit the oxidative surface
layer or penetrate into the reductive subsurface layer.
Physiological Factors Affecting Elemental Accumulation
The most significant physiological process controlling macrophytic accumulation of
nutrients and heavy metals is transport across biological membranes (Kabata-Pendias and
Pendias, 1992). Root uptake and translocation require specialized transport mechanisms
that depend strongly on chemical speciation. Elemental absorption occurs by three major
transport routes, passive diffusion, carrier-mediated pathways involving membrane
components, and active transport driven by a potential gradient (Morrison, 1990;
Alloway, 1995). Physiological differences have been reported among species and among
genotypes within species, with respect to elemental uptake sites and uptake mechanisms
(Outridge and Noller, 1991; Kabata-Pendias and Pendias, 1992).
Other physiological factors reported to affect elemental accumulation include ion
interactions at the root surface, microbial activity, metabolic requirements, tissue storage
capacity, maintenance of osmotic potential, surface area of the root, formation of root
plaques and various root exudates (Outridge and Noller, 1991; Alloway, 1995; Phillips,
1995; Ye et al., 1997a,b,c).
18
Literature Review
There is little information available concerning the levels of nutrients and heavy
metals in the tissues of wetland macrophytes under normal growing conditions.
However, data published on the elemental contents of terrestrial and freshwater plant
species growing in uncontaminated environments can be analogous, and are somewhat
useful for comparison purposes. Trace element data from the tissues of wetland
macrophytes found in constructed wetlands and polluted environments are also discussed
here.
Outridge and Noller (1991) reviewed the published data discussing concentrations of
trace elements in the tissues of freshwater vascular plants from uncontaminated
environments. Their survey included wetland macrophytes and trace elements of interest
to the current study, a summary of the data presented in their review article is listed in
Table 2. They found that manganese had the highest concentrations reported in the
literature for freshwater plants, followed by zinc, molybdenum, copper and lead. Higher
concentrations of gold, arsenic, cadmium, chromium, mercury, nickel, lead, selenium and
uranium were reported in freshwater plants than those reported for terrestrial vegetation.
Concentrations of cobalt, copper, manganese and vanadium were similar in freshwater
and terrestrial plants, and the concentration of zinc was observed to be lower in
freshwater plants. Outridge and Noller (1991) also report that submergent and/or
emergent species had been found to have higher concentrations of arsenic, cadmium,
chromium, cobalt, lead, manganese, molybdenum, nickel, uranium and zinc than other
plant life forms, while floating-leaved species had the lowest concentrations of
19
Table 2: Summary of trace metal concentrations in freshwater plants from
uncontaminated environments (Outridge and Noller, 1991)
Element
n
Ag
As
Cd
Co
Cr
Cu
Hg
Mn
Mo
Ni
Pb
Se
16
22
64
25
58
70
16
77
35
56
64
14
7
16
67
U
V
Zn
Minimum' Maximum
0.05
0.04
0.00
0.04
0.12
0.14
0.02
34
0.14
0.85
0.30
0.10
0.05
0.28
11
1.2
15
11
17
45
55
19
6,880
87
23
35
2.5
1.1
57
250
Median
Mean
Std Dey
95%C.L. 2
0.15
2.7
1.0
0.32
4.0
7.9
0.50
370
12
4.2
6.1
1.0
0.50
3.6
52
0.36
3.2
1.9
3.4
5.4
13
4.1
730
18
6.2
8.1
1.1
0.45
9.1
66
0.39
3.8
2.4
4.9
7.1
13
5.7
1,130
22
5.0
7.2
1.0
0.42
15
48
0.15-0.57
1.5-4.9
1.3-2.5
1.4-5.4
3.6-7.3
9.7-16
1.3-6.9
480-990
11-26
4.9-7.6
6.3-9.9
0.5-1.6
0.06-0.84
1.0-17
54-78
'Units in ug/g dry weight
Confidence limits
2
elements except for copper. Root tissues were found to contain higher concentrations of
most elements compared to aboveground plant parts, with the exception of manganese
which was found at higher concentrations in leaves and stems. Finally, Outridge and
Noller (1991) wrote that the maximum concentrations of trace elements in freshwater
macrophytes from polluted environments were one to two orders of magnitude higher
than levels which were determined to be naturally occurring.
Kabata-Pendias and Pendias (1992) have conducted an extensive review of the
published literature concerning concentrations of trace elements in soils and terrestrial
plants. Table 3 lists approximate concentrations of trace elements found in mature leaf
tissues, generalized for various terrestrial species. The chemical and biological
20
Table 3: Approximate concentrations of trace elements in mature leaf tissue
generalized for various species (Kabata-Pendias and Pendias, 1992)
Element
Deficient'
Sufficient
or Normal
Ag
As
B
Ba
Be
Cd
Co
Cr
Cu
5-30
2-5
F
Hg
Li
Mn
Mo
Ni
Pb
Se
Sn
Sb
Ti
Ti
10-30
0.1-0.3
-
3
30-300
0.2-5
0.1-5
5-10
0.01-2
-
7-50
V
Zn
Zr
l
0.5
1-1.7
10-100
<1-7
0.05-0.2
0.02-1
0.1-0.5
5-30
5-30
10-20
-
0.2-1.5
27-150
-
Excessive
or Toxic
5-10
5-20
50-200
500
10-50
5-30
15-50
5-30
20-100
50-500
1-3
5-50
400-1,000
10-50
10-100
30-300
5-30
60
150
50-200
20
5-10
100-400
15
Tolerable in
Agronomic Crops
100
3
5
2
50
300
50
10
300
Units in ug/g dry weight
properties of nutrients and trace elements discussed by Kabata-Pendias and Pendias are
relevant to the present study. They report that aluminum is an essential element for all
plants, occurring in crops in the range 10-900 ug/g, with aluminum-accumulating species
containing more than1,000 ug/g. Arsenic concentrations of crops grown on
uncontaminated soils are reported to be between 1-1.7 ug/g, with 5-20 ug/g being
excessive or toxic. Cadmium is a non-essential element for plants, although it is
21
absorbed by plant roots and leaves. Normal cadmium concentrations in plants range from
0.05-2.0 ug/g. Most soils contain significant amounts of chromium, although plant
availability is highly limited, common levels of chromium in plants are reported to be
0.1-0.5 ug/g. Cobalt is not known to be an essential element for higher plants, although
there are several reports of the beneficial effects of cobalt on nitrogen fixation. Normal
cobalt concentrations in plants range from 0.02-1.0 ug/g, with 15-50 ug/g being excessive
or toxic. Copper sufficiency in plants is reported to be 5-30 ug/g, with toxicity at 20-100
ug/g. Plants have a strong tendency to hold copper in root tissues, limiting transport
under conditions of deficiency or excess. Shoot tissues usually do not exceed 20 ug/g
copper in species growing under natural conditions, this value is often considered to
indicate the threshold of excessive content. Natural iron concentrations in plants range
from 18-1,000 ug/g, depending on the solubility of iron in the soil. Lead occurs in all
higher plants due to environmental pollution, although it is a non-essential element.
Normal lead concentrations in plants are reported to be 5-10 ug/g. Natural levels of lead
in plants growing in uncontaminated areas are quite constant, ranging from 0.1-10 ug/g
with a mean of 2 ug/g. A wide range of manganese has been reported in plant tissues,
with normal ranges being between 30-300 ug/g. The critical manganese deficiency level
for most plants is 10-30 ug/g, while toxic concentrations of manganese are more variable
depending on plant and soil factors. Normal nickel content of plants growing on
uncontaminated soils are reported to be between 0.1-5 ug/g. Environmental pollution
greatly influences plant concentrations of nickel, tops of plants accumulate nickel in areas
where it is airborne. The essentiality of selenium in plants is still unknown, although
22
plant concentrations have been actively investigated because of selenium's role as both a
micronutrient and a toxin in animal and human nutrition. Normal selenium ranges are
reported to be between 0.01-2 ug/g, with 5-30 ug/g being excessive or toxic. Zinc
concentrations in plants are related to soluble forms available in the soil, and are greatly
influenced by environmental zinc pollution. Normal levels of zinc in plant tissues range
from 27-150 ug/g, with excessive or toxic levels being between 100-400 ug/g (Kabata-
Pendias and Pendias, 1992).
Markert (1994) published trace element contents of a "reference plant", which are
considered to be representative of trace element concentrations for plants in general
(Table 4). Markert's reference plant data is in good agreement with the terrestrial plant
data reported by Kabata-Pendias and Pendias (1992).
Table 4: Trace element content of a "reference plant" (Markert, 1994)
Trace Element
Aluminum (Al)
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Bismuth (Bi)
Boron (B)
Bromine (Br)
Cadmium (Cd)
Cerium (Ce)
Cesium (Cs)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Fluorine (F)
Gallium (Ga)
Gold (Au)
ug/g
80
0.1
0.1
40
0.001
0.01
40
4.0
0.05
0.5
0.2
1.5
0.2
10
2.0
0.1
0.001
Trace Element
ug/g
Iodine (I)
Iron (Fe)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Molybdenum (Mo)
Nickel (Ni)
Selenium (Se)
Silver (Ag)
Strontium (Sr)
Thallium (Tl)
Tin (Sn)
Titanium (Ti)
Tungsten (W)
Uranium (U)
Vanadium (V)
Zinc (Zn)
3.0
150
1.0
200
0.1
0.5
1.5
0.02
0.2
50
0.05
0.2
5.0
0.2
0.01
0.5
50
23
Karpiscak et al. (1997, 1998) report concentrations of nutrients and heavy metals in
the tissues of wetland macrophytes grown in constructed wetland treatment systems at the
Constructed Ecosystems Research Facility (CERF). CERF is a joint project of the Pima
County Wastewater Management Department and The University of Arizona's Office of
Arid Lands Studies, and is comprised of parallel subsurface constructed wetland systems.
The experimental wetlands are planted with identical macrophyte species and receive
either potable water or unchlorinated secondary quality municipal effluent. Average
annual nutrient and heavy metal concentrations are reported for the tissues of Anemopsis
californica, Arundo donax, Baccharis, Fraxinus sp., Populus fremontii, Salix nigra,
Scirpus olneyi and Typha domingensis for samplings throughout 1995 and 1996 (Table
5). Karpiscak et al. (1997, 1998) report elemental concentrations in leaf, root and flower
tissues separately for Anemopsis californica, Scirpus olneyi and Typha dom ingensis
(Table 6).
Karpiscak et al. (1997, 1998) report that the concentrations of total nitrogen,
phosphorous, sodium, manganese and chloride were higher in plants sampled from the
effluent-fed wetland system than from the potable-fed system. Zinc and copper
concentrations were generally greater in plants sampled from the potable-fed system,
with the exception of Anemopsis. Lead was detected at about the same concentration in
both water systems, except for Anemopsis, which concentrated lead in the effluent-fed
system. Nitrate and iron concentrations were approximately the same in plant samples
from both systems, and there was no consistency reported with regard to the
concentrations of total potassium and boron and wetland treatment system.
24
Table 5: Selected chemical parameters in plant tissue samples from potable and effluent-fed
constructed wetland treatment systems (Karpiscak et al., 1997, 1998)
Salbc nigra
Populus fremontii
Fraxinus sp.
Anemopsis californica
Nitrogen
Phosphorous
Potassium
Chloride
Nitrate
Sodium
Iron
Zinc
Copper
Lead
Manganese
Boron
Nitrogen
Phosphorous
Potassium
Chloride
Nitrate
Sodium
Iron
Zinc
Copper
Lead
Manganese
Boron
Nitrogen
Phosphorous
Potassium
Chloride
Nitrate
Sodium
Iron
Zinc
Copper
Lead
Manganese
Boron
Nitrogen
Phosphorous
Potassium
Chloride
Nitrate
Sodium
Iron
Zinc
Copper
Lead
Manganese
Boron
%
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
%
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
1995 Average Concentration
Potable System
Effluent System
2.37
3.21
0.19
0.33
1.48
1.38
723
683
60.8
60.0
299
647
95.0
82.3
57.1
29.1
12.8
7.43
<1.25
<1.25
136
1,039
62.4
48.2
1.78
2.59
0.12
0.38
1.43
1.50
248
330
86.8
71.7
355
1,014
55.4
55.7
55.4
23.6
10.0
4.53
<1.25
<1.25
126
201
51.1
53.6
%
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
%
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
uglg
ug/g
ug/g
No data available, plants not mature.
2.11
0.14
3.70
30,329
1,061
3,080
110
15.6
6.98
1.56
44.3
60.3
4.14
0.43
4.80
38,900
1,371
6,660
135
21.1
6.18
4.86
163
55.9
1996 Average Concentration
Potable System
Effluent System
1.86
3.39
0.10
0.27
1.68
1.59
930
970
<30
32.7
87.8
1,602
158
186
85.5
21.8
9.88
4.97
1.67
2.48
411
857
76.6
54.3
1.87
3.11
0.12
0.41
1.55
1.86
174
524
<30
10.8
269
1,809
133
125
61.9
14.4
7.51
2.45
<5.1
<5.1
148
222
50.6
68.8
0.71
0.88
0.05
0.08
0.57
0.50
239
220
25.0
50.5
<60
<60
60.2
63.3
9.37
5.63
4.97
2.41
<5.1
1.14
14.2
19.5
16.5
19.4
1.90
4.11
0.11
0.46
3.79
4.88
36,160
40,840
186
2,132
7,558
11,824
205
492
17.4
16.3
7.33
4.49
1.38
1.59
63.5
202
61.0
76.9
25
Table 5: Continued
Arundo donctx
Nitrogen
Phosphorous
%
Potassium
Chloride
Nitrate
Sodium
Iron
Zinc
Scirpus olneyi
Copper
Lead
Manganese
Boron
Nitrogen
Phosphorous
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
%
Potassium
Chloride
Nitrate
Sodium
Iron
Zinc
Typha domingensis
Copper
Lead
Manganese
Boron
Nitrogen
Phosphorous
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
%
Potassium
Chloride
Nitrate
Sodium
Iron
Zinc
Baccha ris
Copper
Lead
Manganese
Boron
Nitrogen
Phosphorous
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
%
Potassium
Chloride
Nitrate
Sodium
Iron
Zinc
Copper
Lead
Manganese
Boron
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
1995 Average Concentration
Potable System
Effluent System
2.24
3.03
0.15
0.29
1.87
2.16
6,943
6,941
296
247
253
265
152
110
21.0
19.3
10.5
4.18
8.74
6.13
62.1
112
14.0
22.3
2.21
2.72
0.13
0.25
1.83
1.46
19,729
24,179
105
138
4,131
4,168
83.3
96.9
25.7
22.0
7.81
4.98
<1.25
<1.25
377
1,962
135
115
2.42
2.95
0.15
0.26
1.82
2.11
19,764
19,664
104
116
2,884
3,984
63.1
61.8
14.4
17.9
4.18
9.80
1.44
1.58
273
834
95.4
160
2.06
3.09
0.21
0.46
2.64
2.33
10,180
9,713
362
383
1,376
3,195
96.0
95.7
21.0
32.7
4.54
11.1
2.72
2.36
108
68.7
48.7
75.0
1996 Average Concentration
Potable System
Effluent System
1.80
2.81
0.13
0.24
1.51
2.04
6,406
8,136
125
177
16.0
<60
191
168
15.8
13.0
9.18
7.30
5.45
3.01
179
175
19.8
23.5
2.25
2.98
0.15
0.24
1.54
1.96
16,600
23,680
34.9
47.0
2,974
5,404
155
176
19.2
18.2
7.89
4.80
<5.1
<5.1
702
1,728
131
131
2.43
2.91
0.28
0.15
2.24
2.58
18,540
23,000
47.4
49.8
3,362
4,933
222
146
17.1
14.9
9.12
3.90
2.57
1.29
345
1,075
202
136
2.18
3.34
0.52
0.22
2.61
2.37
9,388
10,392
35.0
242
1,690
3,987
232
429
48.3
20.2
11.2
3.99
<5.1
<5.1
104
106
41.5
62.8
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27
Anernopsis was reported by Karpiscak et al. (1997, 1998) to have the highest
concentrations of most of the chemical parameters studied.
Vymazal (1995) surveyed the literature for concentrations of macronutrients,
micronutrients and trace elements in algae and aquatic and wetland plants. Wetland
plants surveyed by Vymazal included emergent, submergent and floating species, and
many are divided into above and below ground tissues (Table 7). Data presented by
Vymazal are from uncontaminated and contaminated wetland environments, and values
are greater than those reported elsewhere.
Table 7: Elemental concentrations in emergent, submerged and floating-leaved
life forms of aquatic and wetland plants (Vymazal, 1995)
Element
Tissue
Emergent Species'
Arsenic
Boron
AG2
AG
AG
BG3
AG
AG
AG
BG
AG
BG
AG
BG
AG
BG
AG
BG
AG
AG
BG
AG
BG
0.04-12
1.2-100
0.02-11
0.1-16
<1.0-17.2
0.01-6.72
<1-1,900
1.3-81
19-59,000
42-6,900
0.04-657
<0.1-88
13-5,400
13-365
<0.01-2.2
0.01-1.47
<1.0-1,200
0-280
0-52.3
1-337
20-440
Cadmium
Chromium
Cobalt
Copper
h-on
Lead
Manganese
Mercury
Nickel
Selenium
Zinc
'Units in ug/g dry weight
plant tissue
3 Belowground plant tissue
2Aboveground
Submerged Species
Floating Species
0.33-3,700
0.47-959
0.1-32.3
0.5-30
1.06-2,567
5-10,600
0.86-122.2
<1-36.1
3-206
0.27-8,600
0.33-18.6
0-54,500
80-110,000
50-8,440
0.8-7,750
2.7-25,790
73-17,100
400-13,000
<0.01-26.4
0.01-3.8
4-87.3
4-33.9
11.5-650
24-3,224
28
CHAPTER 2: RESEARCH OVERVIEW
This research determined concentration ranges at which micronutrients and heavy
metals naturally exist in the tissues of wetland macrophytes in Arizona. Furthermore,
elemental distributions within the plant root, shoot and leaf parts were measured.
Background data are necessary for evaluating the degree to which nutrients and heavy
metals can be concentrated in constructed wetland systems. Knowledge of background
concentrations will enable us to better understand the effectiveness of engineered
wetlands, and the impact such systems have on our environment.
Site Selection
Seven naturally occurring wetland sites were selected for this research: Empire
Cienega, Canelo Hills Cienega, Patagonia-Sonoita Creek Preserve, Cook's Lake,
St. David Cienega, Bingham Cienega and Agua Caliente Park. Sites chosen for this
research have been classified as natural wetland systems, and most of the plant species
selected for analysis are found at each. These sites are owned and managed by The
Nature Conservancy, The Bureau of Land Management or The Bureau of Reclamation, as
outlined in Table 8. Locations of the selected wetlands in the state of Arizona are
illustrated in Figure 2. Maps detailing directions to the study sites and sampling points
within each site can be found in the appendices.
Empire Cienega is a Resource-Conservation riparian area and marshland located on
the Cienega Creek. Dominant vegetation includes Populus fremontii and Salix
gooddingii, both mature and seedling plants, as well as Typha domingensis, Scirpus
29
Table 8: Selected sites, wetland types and ownership
Site: Empire Cienega
Wetland: Cienega
Owner: The Nature Conservancy
Contact: Dave Gori, (520) 622-3861
Site: Canelo Hills Cienega
Wetland: Cienega
Owner: The Nature Conservancy
Contact: Jeffrey Cooper, (520) 394-2400
Site: Patagonia-Sonoita Creek Preserve
Wetland: Cienega
Owner: The Nature Conservancy
Contact: Jeffrey Cooper, (520) 394-2400
Site: Cook's Lake
Wetland: Wooded swamp, Cattail marsh
Owner: U.S. Bureau of Reclamation
Contact: Diane Laush, (602) 395-5694
Site: St. David Cienega
Wetland: Cattail marsh
Owner: U.S. Bureau of Land Management
Contact: Karen Simms, (520) 722-4289
Site: Bingham Cienega
Wetland: Wooded swamp, Cattail marsh
Owner: Pima County Flood Control District, managed by TNC
Contact: Dave Gori, (520) 622-3861
Site: Agua Caliente Park
Wetland: Developed Cienega
Owner: Pima County
Contact: Evelyn Thorpe, (520) 740-2690
30
31
acutus and Sporobolus sp. Plant communities in this area are classified as ScrubGrassland (143.1), Sonoran Riparian and Oasis Forests (224.5) and Sonoran Interior
Marshland (244.7) using the classification system devised by Brown et al. (1979) and
Minckley and Brown (1982).
Canelo Hills Cienega is located on a small tributary of the Babocomari River, feeding
off of the San Pedro River. A concrete structure at this cienega has created a permanent
pool of water, with predominant vegetation including Prosopis velutina, Populus
fremontii, Salix gooddingii and Scirpus arnericanus. Plant communities include Sonoran
Riparian and Oasis Forests (224.5) and Sonoran Interior Marshland (244.7).
Patagonia-Sonoita Creek Preserve is a riparian habitat with remnant cienegas, located
in the floodplain valley between the Patagonia and Santa Rita mountains. The dominant
vegetation type within this habitat is the Populus fremontii-Salix gooddingii association,
with prominent low-growing Anemopsis californica. The plant communities at
Patagonia-Sonoita Creek Preserve are classified as Sonoran Riparian and Oasis Forests
(224.5) and Sonoran Interior Marshland (244.7).
Cook's Lake, a 32 acre conservation area located 400 meters east of the San Pedro
River, is classified as a spring-fed riparian woodland and marsh. A vegetation analysis
was conducted for Cook's Lake that identified 235 plant species and 11 plant associations
(Baker and Wright, 1996). The dominant vegetation type within the riparian woodland
and marsh is Salix gooddingii, with prominent associations including Larrea tridentata,
Fraxinus velutina , Scirpus acutus, Prosopis velutina, Tamarix ramosissima, Populus
fremontii, Cephalanthus occidentalis, Scirpus americanus and Typha domingensis.
32
Baker and Wright divided the communities into dry, Sonoran Desertscrub (154.1), wet,
Interior Southwestern Deciduous Forests and Woodland (223.2), Sonoran Riparian and
Oasis Forests (224.5), Interior Southwestern Swamp and Riparian Scrub (233.2), Sonoran
Interior Strand (254.7) and Sonoran Interior Marshland (244.7).
St. David Cienega is a cattail marsh and mesquite bosque located near the San Pedro
River. Typha domingensis is the dominant plant species in this protected area, with
prominent Prosopis velutina. Classification of the biotic communities within St. David
includes Sonoran Riparian and Oasis Forests (224.5) and Sonoran Interior Marshland
(244.7).
Bingham Cienega is a wooded swamp and cattail marsh located in the San Pedro
River Valley. This area is heavily vegetated by Prosopis juliflora, Baccharis glutinosa
and Sporobolus airoides, with the wetland being dominated by Typha domingensis and
Lemna spp. Plant communities in this area include Scrub-Grassland (143.1), dry,
Sonoran Desertscrub (154.1), Sonoran Riparian and Oasis Forests (224.5), Sonoran
Interior Marshland (244.7) and Sonoran Inland Submergents (264.7).
Agua Caliente Park, located northeast of Tucson, is a 101-acre aquatic/riparian habitat
surrounded by the Sonoran Desert. A spring feeds three ponds within Agua Caliente
Park, linked to each other by an artificial stream. Vegetation at this park includes
Prosopis velutina, Populus fremontii and Salix gooddingii, classified as a Sonoran
Riparian and Oasis Forest (224.5) community, and Scirpus acutus, Typha domingensis
and Anemopsis californica, classified as a Sonoran Interior Marshland (244.7)
community.
33
Plant Species Selection
Plants selected for this research are species that are commonly used in constructed
wetland systems, or planted nearby, and are identified on the "National List of Plant
Species that Occur in Wetlands" (Reed, 1988). Selected species include Anemopsis
californica (Nutt.) Hook. & Arn. (yerba mansa), Fraxinus velutina (Torr.) (velvet ash),
Lemna spp. (Phil.) (duckweed), Populus fremontii (Wats.) (Fremont cottonwood), Salix
gooddingii (Ball) (Goodding black willow), Salix lasiolepis (Benth.) (Arroyo willow),
Scirpus acutus (Muhl.) Ex Bigelow (hard-stem bulrush), Scirpus americanus (Pers.)
(three-square bulrush) and Typha domingensis (Pers.) (southern cattail). Reed et al.
(1988) have developed a system of categories for assessing the occurrence of plants in
wetland environments, as outlined in Table 9. Obligative wetland plants almost always
occur in wetlands, with a probability of greater than 99 percent, and facultative wetland
plants are usually found in wetlands, with a probability of 67-99 percent. A "+" or "—" is
often applied to the categories to indicate that the species is found at the higher or lower
end of the probabilities. With the exception of Fraxinus, all of the species included in
this study are categorized as either obligative or facultative wetland plants (Table 10).
Elemental Analysis
Elements selected for analysis in this study are micronutrients and heavy metals that
are prevalent in wastewater and can be toxic to plants and animals at elevated levels.
Soil, water and plant tissues were sampled and analyzed for aluminum, arsenic, cadmium,
34
Table 9: System of categories for determining the occurrence of
wetland plants (Reed et al., 1988b)
Category
Occurrence in Wetland Environment
OBL Obligative Wetland Plant
> 99% of the time
FACW Facultative Wetland Plant
67-99% of the time
FAC Facultative Plant
34-66% of the time
FACU Facultative Upland Plant
<33% of the time
UPL Upland Plant
almost never
Table 10: Selected plant species and their wetland categories
(Reed et al., 1988; Baker and Wright, 1996)
Scientific Name
A nemopsis californica
Fraxinus velutina Lemna spp
Populus fremontii
Salix gooddingii
Salix lasiolepis
Scirpus acutus
Fremont cottonwood
Scirpus americanus
Typha domingensis
Common Name
yerba mansa
velvet ash
duckweed
Wetland Category
OBL
FAC+
OBL
Goodding black willow
arroyo willow
hard-stem bulrush
three-square bulrush
southern cattail
FACW
OBL
FACW
OBL
OBL
OBL
35
chromium, cobalt, copper, iron, lead, manganese, nickel, selenium and zinc. The term
nutrient describes an essential element which is "required by an organism to build living
tissue and maintain the chemical reactions of the life process" (Pais and Jones, 1997).
Macronutrients are essential elements that an organism needs in relatively large
quantities, and micronutrients are needed in relatively small quantities. The term trace
element is used for non-essential elements that are found at low concentrations in plant
tissues. Heavy metal is a term referring to the metal trace elements, generally describing
metallic elements with high atomic weights and similar health effects. Pais and Jones
(1997) have stated that the heavy metal group is "somewhat poorly defined" with a range
down to atomic weight 24 (chromium), and includes several non-metals such as arsenic
and selenium. Table 11 lists the form, classification and biological functions of the
elements selected for analysis in this study.
Data Analysis
Concentrations of 12 elements have been determined in the tissues of nine wetland
macrophyte species, sampled from seven study sites. Data analysis was done by element,
with separate sections used to discuss the concentration ranges, means and
95% confidence limits for each element in the tissues of selected plant species. Data is
reported below a minimum detection limit for samples with no nutrient and heavy metal
concentrations detectable. For statistical analysis, values below the minimum detection
limit are assumed to be halfway between zero and the minimum detection limit, assuming
these values are normally distributed (Bilisoly et al., 1997; Clarke, 1998).
36
Table 11: Selected elements and their form, classification and
biological functions (Modified from Pais and Jones, 1997)
Element
Form
Classification
Biological Function
Aluminum
metal
trace element
Control of colloidal properties in the
cell
Arsenic
non-metal
trace element
Metabolism of carbohydrates
Cadmium
metal
trace element
None
Chromium
metal
trace element
None
Cobalt
metal
trace element
Combines with proteins and enzymes
for catalytic properties
Copper
metal
micronutrient
Oxidation, photosynthesis and
metabolism of proteins
Iron
metal
micronutrient
Photosynthesis, nitrogen fixation and
protein and dehydrogenase
•
constituent
None
Lead
metal
Manganese
metal
trace element
micronutrient
Nickel
metal
micronutrient
Hydrogenase reactant and nitrogen
translocation
Selenium
non-metal
trace element
Combines with proteins and enzymes
for catalytic properties
Zinc
metal
micronutrient
Metabolism of carbohydrates and
proteins
Photoproduction of oxygen and
nitrate reduction
37
Coefficient of variability (C.V.), number of samples (n) and percent censored data are
also reported for each element. A complete plant data set listing plant samples by study
site can be found in the appendices.
Plant analysis was done by plant part, and data are reported separately for root, shoot
and leaf tissues. Plant life forms are also included, referring to the structure of the
species, with terrestrial herb (H), tree (T), shrub (S), free-floating floating-leaved (F) and
rooted emergent (E) macrophyte species. For discussion, plants are often grouped by
plant part and life form. Soil and water samples were collected at the same sampling
points, and are also discussed with the plant data.
38
CHAPTER 3: METHODS AND TECHNIQUES
Sample Collection
Soil, water and plant tissue samples were collected at seven natural wetland sites
during May 1998, as outlined in Table 12. Three sampling points were selected within
each site where standing water was present, and soil and water grab samples were
collected at these sampling points. Plant tissue samples were collected within a fivemeter radius of the soil and water sampling points at each site. At the Patagonia-Sonoita
Creek Preserve and St. David Cienega wetland sites, only two sampling points were
selected due to insufficient plant growth. Agua Caliente Park was treated as one
sampling point because plants were found in clusters by species throughout the park.
Table 12: Sampling schedule.
Site
Sampling Date
Empire Cienega
May 13, 1998
Canelo Hills Cienega
May 14, 1998
Patagonia-Sonoita Creek Preserve
May 14, 1998
Cook's Lake
May 15, 1998
St. David Cienega
May 19, 1998
Bingham Cienega
May 23, 1998
Agua Caliente Park
May 23, 1998
39
A trowel was used to collect the top 10 cm of soil at each sampling point. In places
where a layer of peat was covering the soil, the peat was removed and the soil sample was
taken from below the peat material. Soil samples were placed in Ziplock bags and then in
an ice chest for transporting. Water samples were collected in 500 mL, acid-rinsed
Nalgene bottles and placed in an ice chest for transporting. A Horiba U-10 water quality
meter was used to determine the temperature, pH and electrical conductivity (EC) of the
ambient water at each sampling point.
Plant tissue samples were collected in three aliquots around each sampling point, and
then composited to represent that point. Root samples were dug from the soil using a
trowel, and rinsed in the field with deionized water. Shoot samples were cut at a height
of 2 cm above the soil surface with clippers. Leaf samples were collected by clipping
clusters of leaves throughout three trees near the designated sampling points. Plant
samples were placed in paper bags for transport to the laboratory. A specimen of the
plant species sampled at each site was preserved in a field press, and later identified at the
University of Arizona herbarium. Table 13 indicates the presence of the selected plant
species at each of the seven study sites.
Sample Preparation
In the laboratory, soil samples were spread out on trays and air-dried, then passed
through a 2 mm sieve. Residual plant material was removed from the soil samples during
the sieving process. Soil samples were then acid digested using concentrated,
40
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41
trace-metals grade nitric acid in a CEM closed-vessel microwave oven (EPA method
3051, modified). Microwave digestion procedures are advantageous because they reduce
the loss of reagents and sample, and obtain a more complete oxidation of the sample
material allowing for total metal determination (Greenberg et al., 1992). 5MA1 soil
standards, sample duplicates and reagent blanks were included in each digestion batch to
assure appropriate quality control. Acid digested samples were stored in 30 mL Nalgene
bottles at room temperature.
Water samples were filtered in the laboratory with #1 Whatman filter paper, then
acidified with concentrated, trace-metals grade nitric acid to a pH of less than 2. Samples
were stored in 500 mL Nalgene bottles at room temperature. Filtration and acidification
of water samples allows for the determination of dissolved metal species (Greenberg et
al., 1992).
Plant tissue samples were gently rinsed with deionized water in the laboratory, then
placed in a drying oven at 60° C for 24 hours. Dried plant material was ground using a
Wiley-mill fitted with a 40-mesh screen, and stored in coin envelopes in the drying oven.
Ground plant material was acid digested using concentrated, trace-metals grade nitric acid
and hydrogen peroxide in a CEM closed-vessel microwave oven (EPA method 3052,
modified) in preparation for the determination of total metals. National Institute of
Standards and Technology (NIST) pine needle and tomato leaf standards, sample
duplicates, and reagent blanks were included in each digestion batch to assure appropriate
quality control.
42
Sample Analysis
Sample were analyzed for micronutrients and heavy metals at the Soil, Water and
Plant Analysis Laboratory at the University of Arizona using a Leeman Labs UV1000
Inductively Coupled Plasma Optical Emission Spectrometer (ICP/OES). Further
elemental analysis was done at the University of California, Riverside in the Department
of Soil and Environmental Sciences. Instrumentation at the University of California,
Riverside included a Perkin-Elmer 5000 Atomic Absorption Spectrometer (AAS) with
hydride vapor generation, a Perkin-Elmer 3000DV Optima ICP/OES, and a VG
PlasmaQuad 2 Inductively Coupled Plasma Mass Spectrometer (ICP/MS).
Soil and plant tissue samples were analyzed for total concentrations of aluminum, iron
and manganese at the University of Arizona and at the University of California, Riverside
by ICP/OES (EPA method 6010B, modified), and good agreement was found between
analysis at both universities. Concentrations of aluminum, iron and manganese observed
in soil and plant samples are high, and easily detectable by optical emission spectrometry.
ICP/MS was used to determine trace amounts of total arsenic, cadmium, chromium,
cobalt, copper, nickel, lead and zinc in soil, plant tissue and water samples, and total
aluminum, iron and manganese concentrations in water samples (EPA method 6020,
modified). Selenium determination was done by conversion to the volatile hydride form
by sodium borohydride, and aspiration into an AA (EPA method 7742, modified).
43
Minimum detection limits were determined for each element by analysis of 10
replicates of the lowest concentration calibration standard, then multiplying the standard
deviation of the replicates by 10 (EPA method detection limit, modified). Quality control
consisted of the analysis of National Institute of Standards and Technology (NIST) and
SMA1 standards, analysis of reagent blanks, calibration with certified standards, and
analysis of sample duplicates. Certified NIST standards, with concentrations near the
sample levels, were analyzed at 10 percent of the total sample volume and maintained
within 10 percent of the known values. Reagent blanks were analyzed at five percent of
the total sample volume to monitor the purity of the reagents used, and serve as overall
procedural blanks. Certified standards were used to calibrate the instruments daily.
Sample duplicates were analyzed at five percent of the total sample volume, and were
maintained within 10 percent of the known concentrations for precision.
44
CHAPTER 4: RESULTS AND DISCUSSION
Aluminum
The mean concentration of aluminum observed in naturally occurring wetland
macrophytes in Arizona was 740 ug/g (Table 14). Anemopsis californica had the highest
aluminum content of the plant species sampled in this study, with a mean concentration
of 2,312 ug/g in the leaf tissues and 2,151 ug/g in the roots (Table 15). A high mean
aluminum value for Anemopsis californica is due to a single specimen obtained from St.
David Cienega, with an aluminum concentration of 11,660 ug/g. Lemna sp. and roots of
the emergent macrophytes Scirpus acutus, Scirpus americanus and Typha domingensis
also concentrated aluminum to a high degree, with ranges of 476-2,041 ug/g for Lemna
sp. and 102-8,641 ug/g for the roots of the three emergent species. Emergent
macrophytes concentrated aluminum up to ten times greater in root tissues than in shoot
tissues, with mean concentrations of 1,238 ug/g in the roots and 217 ug/g in the shoots.
Tree and shrub leaves contained the lowest levels of aluminum, with a concentration
range of <64.4-304 ug/g.
Aluminum concentrations in water samples were all below the minimum detection
limit, 500 ug/L (Table 16). The EPA has established the Criteria Maximum
Concentration (CMC) for total aluminum in surface water to be 750 ug/L to avoid
harmful effects to aquatic organisms (EPA, 1998). Aluminum concentrations in water
samples for this study are below levels recommended by the EPA.
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Aluminum concentrations observed in soil samples ranged from 5,985-26,400 ug/g,
with a mean concentration of 15,790 ug/g (Table 17). The highest aluminum soil
concentrations were sampled from Cook's Lake, which can be correlated to significantly
higher aluminum concentrations in the root and shoot tissues of Scirpus acutus and
Scirpus americanus.
Anemopsis californica, Lemna sp. and Scirpus americanus can be considered
accumulators of aluminum according to Kabata-Pendias and Pendias (1992), who report
accumulators as species containing more than 1,000 ug/g of aluminum in their tissues.
All other species analyzed for aluminum in this study fall within normal ranges reported
for terrestrial plants, 10-900 ug/g (Kabata-Pendias and Pendias, 1992; Markert, 1994). In
all samples, except for one specimen of Anemopsis californica, aluminum was found at
higher concentrations in the root tissues than in the shoots and leaves. Aluminum is
reported to concentrate in the roots of many plant species, with translocation to plant
shoots reflecting aluminum tolerance (Kabata-Pendias and Pendias, 1992).
Arsenic
The mean concentration of arsenic observed in naturally occurring wetland
macrophytes in Arizona was 0.638 ug/g (Table 14). Lemna sp. was determined to have
the highest arsenic concentration, with a range of 2.80-6.23 ug/g and a mean of 4.51 ug/g
(Table 18). Anemopsis californica was found to have higher arsenic concentrations in
leaf tissues than root tissues, with means of 1.00 ug/g and 0.721 ug/g respectively.
Conversely, arsenic concentrations were greater in the roots than the shoots of all
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emergent species sampled, with mean concentrations of 1.08 ug/g and 0.200 ug/g
respectively. Relatively high arsenic levels were observed in the root tissues of emergent
species Scirpus americanus and Typha domingensis, with means of 1.72 ug/g and 1.17
ug/g each. The tree species Populus fremontii had a mean arsenic concentration of 0.216
ug/g, while no arsenic was detected in the tree species Fraxinus velutina, Salix
gooddingii and the shrub Salix lasiolepis.
Arsenic was detected in all of the water samples in this study, with a range of 7.4226.6 ug/L and a mean of 12.3 ug/L (Table 16). The highest arsenic concentrations in
water samples were from St. David Cienega, with 25.8 ug/L determined at site 1 and
26.6 ug/L at site 2. Elevated arsenic levels in water samples from St. David Cienega
correlated with the maximum arsenic concentration found in a single plant specimen,
8.25 ug/g, in the root tissue of Scirpus americanus at the same site. EPA (1998) has
established the CMC for arsenic in surface waters to be 340 ug/L, arsenic concentrations
determined in this study are well within permissible levels.
In soil samples, arsenic concentrations were determined to range from 3.12-155 ug/g
(Table 17). The highest soil concentration, 155 ug/g, was observed in a sample from
Canelo Hills Cienega, while the next greatest soil arsenic concentration was only 34.6
ug/g.
In this study, Anemopsis californica, Lemna sp., Scirpus americanus and Typha
domingensis accumulated arsenic to a greater degree than the range Kabata-Pendias and
Pendias (1992) report to be normal for terrestrial plants, 1-1.7 ug/g. Markert (1994) lists
a much lower arsenic concentration for plants, 0.1 ug/g, similar to 63 percent of the
52
arsenic data in this study which was censored because values were below the minimum
detection limit of 0.30 ug/g. Concentration means of all species analyzed fell within the
reported 95% confidence limits for arsenic in freshwater vascular plants, 1.5-4.9 ug/g
(Outridge and Noller, 1991). The mean concentration determined for arsenic in naturally
occurring wetland macrophytes, 0.638 ug/g, was quite a bit lower than the mean
concentration reported by Outridge and Noller for freshwater vascular plants, 3.2 ug/g
(1991).
Cadmium
The mean concentration of cadmium observed in naturally occurring wetland
macrophytes in Arizona was 0.195 ug/g (Table 14). Lemna sp. was determined to have
the highest cadmium content, with a range of 0.971-1.55 ug/g and a mean of 1.26 ug/g
(Table 19). Anemopsis californica and Scirpus americanus both had higher cadmium
concentrations in root tissues than leaves and shoots, with means of 0.185 ug/g and 0.139
ug/g in roots and 0.100 ug/g and <0.16 ug/g in leaves and shoots respectively. In
contrast, shoots of the emergent species Typha domingensis concentrated cadmium to a
greater degree than the roots, with means of 0.159 ug/g and 0.111 ug/g respectively.
Cadmium was not detected in the tissues of the emergent species Scirpus acutus. Tree
and shrub species demonstrated an ability to acquire cadmium, a range of <0.16-0.989
ug/g was determined in leaves, although no cadmium was detected in samples of
Fraxinus velutina.
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Cadmium concentrations in water samples were all below the minimum detection
limit, 5.0 ug/L (Table 16), which is also the EPA's established maximum contaminant
level (MCL) for drinking water (EPA, 1998). The CMC suggested for cadmium is 4.3
ug/g, slightly lower than drinking water standards (EPA, 1998). Cadmium was also
below the minimum detection limit for soil samples in this study, 2.5 ug/g (Table 17).
Lemna sp., the only floating-leafed species sampled in this study, contained
significantly higher cadmium concentrations than any other life form, which is
contradictory to that reported by Outridge and Noller (1991). The mean concentration of
cadmium determined in naturally occurring wetland macrophytes, 0.195 ug/g, is similar
to that reported by Outridge and Noller (1991) for freshwater vascular plants, 1.9 ug/g,
and Kabata-Pendias and Pendias (1992) for terrestrial plants, 0.05-0.2 ug/g.
Chromium
The mean concentration of chromium observed in naturally occurring wetland
macrophytes in Arizona was 1.04 ug/g (Table 14). Lemna sp. was found to have the
highest chromium concentration, with a range of 1.77-2.78 ug/g and a mean of 2.28 ug/g
(Table 20). The terrestrial herb Anemopsis californica was determined to have a mean
concentration of 1.85 ug/g chromium in its root tissues, and a mean concentration of 2.09
ug/g in its leaves. Emergent macrophytes, Scirpus acutus, Scirpus americanus and Typha
domingensis, concentrated chromium to a greater degree in root than shoot tissues, with a
mean root concentration of 1.13 ug/g and a mean shoot concentration of 0.721 ug/g for
•
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56
all three species. Tree and shrub species concentrated chromium to the lowest degree,
with a range of 0.238-2.01 ug/g and mean of 0.632 ug/g.
Chromium concentrations in water samples were all below the minimum detection
limit, 5.0 ug/L (Table 16). EPA (1998) has established the surface water CMC for
dissolved chromium species to be 570 ug/L for Cr III and 16 ug/L for the more toxic Cr
VI. Chromium concentrations determined in natural wetlands for this study were within
a permissible range.
In soil samples, chromium concentrations ranged from 10.3-50.4 ug/g, with a mean of
23.5 ug/g (Table 17). The highest soil chromium concentration was sampled from St.
David Cienega, where the maximum chromium concentration found in a single specimen,
7.14 ug/g, occurred in the leaves of Anemopsis californica.
Chromium concentrations determined for wetland macrophytes in this study were
higher than the range of 0.1-0.5 ug/g reported for terrestrial plants by Kabata-Pendias and
Pendias (1992). The mean chromium concentration determined in naturally occurring
wetland macrophytes was 1.04 ug/g, while that reported for freshwater vascular plants is
5.4 ug/g (Outridge and Noller, 1991). Markert (1994) lists a chromium concentration of
1.5 ug/g for all plants. Elevated chromium contents are reported in the literature for root
tissues, which was observed only in emergent macrophyte species in this study (KabataPendias and Pendias, 1992).
57
Cobalt
The mean concentration of cobalt observed in naturally occurring wetland
macrophytes in Arizona was 0.317 ug/g (Table 14). Lemna sp. had the highest cobalt
content, with a range of 1.11-2.69 ug/g and a mean of 1.90 ug/g (Table 21). Anemopsis
californica was found to have a mean cobalt concentration of 0.683 ug/g in the leaf
tissues and 0.586 ug/g in the roots. Emergent macrophytes analyzed in this study had
cobalt concentrations up to six times higher in roots than in shoot tissues, with means of
0.316 ug/g and 0.093 ug/g respectively for all three species. Tree and shrub species were
found to have a cobalt range of <0.135- 1.19 ug/g, and no cobalt was detected in the
species Fraxinus velutina.
Cobalt concentrations in water samples were all below the minimum detection limit,
5.0 ug/L (Table 16). There are no regulatory standards established by the EPA for cobalt.
In soil samples, cobalt concentrations ranged from 3.86-20.5 ug/g, with a mean value of
11.4 ug/g (Table 17). The highest cobalt concentrations determined in soil samples were
from Cook's Lake, which correlated with significantly higher cobalt concentrations in the
tissues of Scirpus acutus and Scirpus americanus from the same site.
The mean concentration of cobalt determined in naturally occurring wetland
macrophytes was 0.317 ug/g, quite a bit lower than the mean reported by Outridge for
freshwater vascular plants, 3.4 ug/g (1991). Cobalt concentrations reported as normal for
terrestrial plants are 0.02-1 ug/g (Kabata-Pendias and Pendias, 1992) and 0.2 ug/g
(Markert, 1994). In this study, Lemna sp. was the only species that accumulated cobalt to
a greater degree than that which is reported for terrestrial plants.
58
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59
Copper
The mean concentration of copper observed in naturally occurring wetland
macrophytes in Arizona was 5.40 ug/g (Table 14). Lemna sp. concentrated copper to the
highest degree, with a range of 23.3-41.7 ug/g and a mean of 32.5 ug/g (Table 22).
Anemopsis californica had a mean copper concentration of 9.81 ug/g in its roots and 6.12
ug/g in shoot tissues. The emergent macrophyte species Scirpus americanus and Typha
domingensis concentrated copper to a high degree in root tissues, with means of 9.40 ug/g
and 9.50 ug/g respectively, while the shoot tissues had lower mean copper concentrations
of 2.58 ug/g and 4.32 ug/g. Scirpus acutus had a mean copper concentration of 1.99 ug/g
in its roots, while no copper was detected in its shoot tissues. Tree and shrub leaves were
found to have copper concentrations ranging from <1.6-11.7 ug/g and a mean of 2.17
ug/g, with the highest concentrations determined in species of Populus fremontii and
Salix gooddingii.
Copper concentrations in water samples were all below the minimum detection limit,
50.0 ug/L (Table 16). EPA (1998) has suggested 1,300 ug/L as a drinking water MCL
goal, while the surface water CMC is 13 ug/L. In soil samples, copper concentrations
ranged from <25.0-101 ug/g, with a mean of 45.5 ug/g (Table 17). The highest soil
copper concentrations were found at Bingham Cienega, a natural wetland located
adjacent to a copper mine, and site 3 of Empire Cienega. The tree species Salix
gooddingii and Populus fremontii, emergent macrophytes Typha domingensis and Scirpus
americanus, and Anemopsis californica had significantly higher copper concentrations at
the Bingham Cienega site.
60
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In this study, all species except for Lemna sp. fell below or within the reported
normal copper range for terrestrial plants, 5-30 ug/g (Kabata-Pendias and Pendias, 1992;
Markert, 1994), and the 95% confidence limits for freshwater vascular plants, 9.7-16 ug/g
(Outridge and Noller, 1991). The mean concentration of copper determined in naturally
occurring wetland macrophytes, 5.40 ug/g, was lower than the mean reported for
freshwater vascular plants, 13 ug/g (Outridge and Noller, 1991). In all samples, copper
was found at higher concentrations in root tissues than in shoots and leaves, which is
consistent with that reported in the literature (Kabata-Pendias and Pendias, 1992).
Lemna sp. was able to accumulate concentrations greater than 20 ug/g in its tissues,
indicating excessive content (Kabata-Pendias and Pendias, 1992).
Copper concentrations determined in naturally occurring wetland macrophytes were
similar to those reported by Karpiscak et al. (1997, 1998) for Anemopsis californica
leaves grown in a potable-fed constructed wetland system, and Populus frernontii and
Typha domingensis shoots grown in an effluent-fed constructed wetland system
(Figure 3). Fraxinus sp., Salix sp., Scirpus americanus roots and shoots and Typha
domingensis roots sampled from naturally occurring wetlands were determined to have
lower copper concentrations than those reported for constructed wetland systems fed
effluent and potable waters (Karpiscak et al., 1997, 1998). As determined in the present
study, Anemopsis californica, Scirpus americanus and Typha domingensis are reported
by Karpiscak et al. (1997, 1998) to concentrate copper to a higher degree in root tissues
than in shoots or leaves in constructed wetland systems.
62
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63
Iron
The mean concentration of iron observed in naturally occurring wetland macrophytes
in Arizona was 569 ug/g (Table 14). Roots of Scirpus americanus had the highest iron
concentration, with a concentration range of 162-9,153 ug/g and a mean of 2,082 ug/g
(Table 23). Anemopsis californica also concentrated high levels of iron, with a range of
123-4,938 ug/g and means of 1,257 ug/g in root tissues and 1,030 in leaves. The
emergent species Scirpus acutus, Scirpus arnericanus and Typha domingensis
concentrated iron up to eight times higher in root tissues than in shoots, with means of
1,185 ug/g and 169 ug/g for root and shoot tissues respectively. Lemna sp. was
determined to have a mean iron concentration of 864 ug/g. Tree and shrub species
Fraxinus velutina, Populus fremontii, Salix gooddingii and Salix lasiolepis concentrated
the least amount of iron, with a range of 44.1-176 ug/g in leaf tissues and a mean
concentration of 109 ug/g.
Most water samples in this study were determined to have iron concentrations below
the minimum detection limit, 100 ug/L (Table 16). EPA does not list drinking water
MCL or surface water CMC values for iron, although a Criterion Continuos
Concentration (CCC) for surface waters is suggested to be 1,000 ug/L to avoid
deleterious effects to aquatic organisms (EPA, 1998). Sites that had detectable iron
concentrations in water samples include Canelo Hills Cienega, Cook's Lake, St. David
Cienega and Bingham Cienega. Site 3 of Cook's Lake had an iron concentration of
169 ug/L, which correlated with maximum iron concentrations in plant tissue of the
species Typha domingensis and the roots of Anemopsis californica.
64
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In soil samples, iron concentrations ranged from 7,753-63,393 ug/g, with a mean
concentration of 20,682 ug/g (Table 17). Agua Caliente Park had the lowest soil iron
concentration, 7,753 ug/g, the next highest was 13,586 ug/g.
In this study, mean iron concentrations determined for Anemopsis californica and
Scirpus americanus were higher than iron concentrations reported for crops and other
terrestrial plants, 18-1,000 ug/g (Kabata-Pendias and Pendias, 1992; Markert, 1994). All
other wetland macrophyte species analyzed in this study fell within the reported range for
iron in terrestrial plants.
Iron concentrations determined in naturally occurring samples of Populus fremontii
were very similar to those reported by Karpiscak et al. (1997, 1998) for the species grown
in effluent-fed and potable-fed constructed wetland systems (Figure 4). Anemopsis
californica, Fraxinus sp. and the shoots of Typha domingensis were determined to have
greater iron concentrations in naturally occurring samples than that which is reported for
the same species grown in constructed wetlands (Karpiscak et al., 1997, 1998). Salix sp.
and Typha domingensis roots were determined to have lower iron concentrations in
naturally occurring plants than that which is reported for those grown in constructed
wetland systems (Karpiscak et al., 1997, 1998). Naturally occurring root and shoot
samples of Scirpus americanus were determined to have greater concentrations of iron
than those sampled from potable-fed constructed wetland systems, and lower
concentrations of iron than samples from effluent-fed constructed wetland systems
(Karpiscak et al., 1997, 1998).
66
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Lead
The mean concentration of lead observed in naturally occurring wetland macrophytes
in Arizona was 2.57 ug/g (Table 14). Lemna sp. had the highest concentration of lead,
with a range of 1.06-33.0 ug/g and a mean of 17.0 ug/g (Table 24). Anemopsis
californica was determined to have a lead concentration range of <0.16-7.79 ug/g, and
concentration mean of 3.36 ug/g in root tissues and 2.15 ug/g in leaves. The emergent
species Scirpus americanus concentrated lead a factor of forty times higher in root tissues
than in shoots, with mean concentrations of 10.1 ug/g and 0.249 ug/g respectively.
Scirpus acutus was also found to have greater lead concentrations in root tissues than in
shoots, with concentration means of 0.422 ug/g and 0.113 ug/g respectively. In contrast,
Typha domingensis concentrated lead to a much higher degree in its shoots than root
tissues, with means of 2.95 ug/g in the shoots and 0.811 ug/g in the roots. A
concentration range of <0.16-18.8 was determined for the tree species. Populus fremontii
and Salix gooddingii had the highest lead concentrations, while no lead was detected in
leaves of the shrub Salix lasiolepis.
Lead concentrations in water samples were all below the minimum detection limit,
5.0 ug/L (Table 16). EPA (1998) has suggested the CMC for lead in surface waters to be
65 ug/L. Lead concentrations determined in natural wetlands for this study were within a
permissible range.
In soil samples, lead values were determined to range from 6.31-65.9 ug/g, with a
mean of 29.0 ug/g (Table 17). Patagonia-Sonoita Creek Preserve had the two highest
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69
soil-lead concentrations, 65.9 ug/g at site 1 and 59.7 ug/g at site 2, which did not correlate
to unusually high lead concentrations in plant tissue samples from this site.
The mean concentration of lead determined in this study for naturally occurring
wetland macrophytes, 2.57 ug/g, was lower than that which is reported by Outridge and
Noller (1991) for freshwater vascular plants, 8.1 ug/g. Markert (1994) reports a normal
lead concentration of 1.0 ug/g for plants in general, while Kabata-Pendias and Pendias
(1992) report a normal range of lead in terrestrial plants to be 5-10 ug/g. In this study,
the concentration means of all species analyzed except for Lemna sp. and Scirpus
americanus fell within the reported range for lead in terrestrial plants. High lead
concentrations determined in the tissues of Lemna sp. and Scirpus americanus may
indicate that they are lead accumulators.
Lead concentrations determined in naturally occurring samples of Populus fremontii
and Salix sp. were similar to those reported by Karpiscak et al. (1997, 1998) for the same
species grown in effluent-fed and potable-fed constructed wetland systems (Figure 5).
Anemopsis californica leaves and Typha domingensis shoots were determined to have
greater lead concentrations in naturally occurring samples than that which is reported for
the same species grown in constructed wetlands (Karpiscak et al., 1997, 1998).
Anemopsis californica roots, Fraxinus sp., Scirpus americanus roots and shoots and
Typha domingensis roots were determined to have lower lead concentrations in naturally
occurring plants than is reported for those grown in constructed wetland systems
(Karpiscak et al, 1997, 1998).
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Manganese
The mean concentration of manganese observed in naturally occurring wetland
macrophytes in Arizona was 747 ug/g (Table 14). Lemna sp. was determined to have the
highest manganese content, with a range of 2,191-13,023 ug/g and a mean of 7,607 ug/g
(Table 25). The tree species Salix gooddingii had unusually high concentrations of
manganese in it's leaf tissues, with a range of 87.7-2,137 ug/g and a concentration mean
of 1,091 ug/g. Scirpus acutus had an unusually high manganese content in its shoots,
with a mean concentration of 1,052 ug/g. The emergent species Scirpus acutus, Scirpus
arnericanus and Typha domingensis were found to have higher manganese concentrations
in shoot tissues than in root tissues, with concentration means of 842 ug/g and 668 ug/g
for roots and shoot tissues respectively. A mean concentration of 214 ug/g was
determined for manganese in the root tissues of Anernopsis californica, with a mean of
108 ug/g for the leaves. The shrub species Salix lasiolepis was determined to have a
mean manganese concentration of 166 ug/g, while the trees Fraxinus velutina and
Populus fremontii had means of only 46.2 ug/g and 59.7 ug/g respectively.
Most water samples in this study were determined to have manganese concentrations
below the minimum detection limit, 10.0 ug/L (Table 16). There are currently no surface
or drinking water standards established by the EPA for the regulation of manganese.
Sites that had detectable manganese concentrations include Empire Cienega, Canelo Hills
Cienega and Bingham Cienega.
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73
In soil samples, manganese values were determined to range from <20.0-30,936 ug/g,
with a mean of 2,445 ug/g (Table 17). The highest soil manganese concentration,
30,936 ug/g, was sampled from Canelo Hills Cienega and correlates with high manganese
concentrations in the tissues of Scirpus acutus at this site.
Lemna sp., Salix gooddingii, Scirpus acutus, Scirpus americanus and Typha
domingensis all had mean manganese concentrations greater than that which is reported
for crops and terrestrial plants, 30-300 ug/g (Kabata-Pendias and Pendias, 1992; Markert,
1994). The mean concentration of manganese determined in naturally occurring wetland
macrophytes was 747 ug/g, similar to that reported by Outridge and Noller (1991) for
freshwater vascular plants, 730 ug/g. A broad range is reported for manganese in the
tissues of freshwater vascular plants, 34-6,880 ug/g (Outridge and Noller, 1991), all
species analyzed in this study had manganese concentrations within the reported range
except for Lemna sp., with a concentration mean of 7,607 ug/g. Outridge and Noller
(1991) report that floating-leaved species accumulate the lowest levels of manganese,
which was not observed in the present study. Lemna sp. accumulated higher
concentrations of manganese than any other life form.
Concentrations of manganese reported by Karpiscak et al. (1997, 1998) for effluentfed constructed wetlands generally had the highest plant tissue concentrations of
manganese (Figure 6). Manganese concentrations determined in naturally occurring
samples of Anemopsis californica, Fraxinus sp., Salix sp., Scirpus americanus roots and
shoots, and Typha domingensis shoots were greater than those reported for the same
species in potable-fed constructed wetland systems (Karpiscak et al., 1997, 1998).
74
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75
Naturally occurring samples of Populus fremontii were determined to have lower
manganese concentrations than those reported for potable-fed constructed wetland
systems (Karpiscak et al., 1997, 1998).
Nickel
The mean concentration of nickel observed in naturally occurring wetland
macrophytes in Arizona was 8.94 ug/g (Table 14). Lemna sp. was determined to have the
highest nickel concentration, with a range of 12.6-205 ug/g and mean of 109 ug/g (Table
26). Anemopsis californica concentrated nickel to a greater degree in its leaf tissues than
roots, with concentration means of 7.99 ug/g and 5.51 ug/g respectively. Emergent
macrophyte species Scirpus acutus and Scirpus americanus had higher nickel
concentrations in root tissues than in shoots, with means of 1.62 ug/g and 0.585 ug/g
respectively in Scirpus acutus, and 21.0 ug/g and 1.73 ug/g in Scirpus americanus.
Similar nickel concentrations were determined in the root and shoot tissues of Typha
domingensis, with concentration means of 3.27 ug/g in the roots and 3.33 ug/g in the
shoots. Tree species had a range of nickel from <0.54-143 ug/g, the species Populus
fremontii and Salix gooddingii had the highest concentrations, 11.5 ug/g and 11.4 ug/g
respectively.
Nickel concentrations in water samples were all below the minimum detection limit,
5.0 ug/L (Table 16). The surface water CMC listed for nickel is 470 ug/L (EPA, 1998),
nickel concentrations determined in natural wetlands for this study were well within a
permissible range.
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In soil samples, nickel was determined in a concentration range from <10.0-38.7 ug/g,
with a mean of 17.3 ug/g (Table 17). The highest soil nickel concentrations were
sampled from Cook's Lake, which correlated with elevated nickel concentrations in the
tissues of Scirpus acutus.
Anemopsis californica, Lemna sp., Populus fremontii, Salix gooddingii and Scirpus
americanus all had mean nickel concentrations greater than that which is reported for
terrestrial plants by Kabata-Pendias and Pendias (1992), 0.1-5 ug/g, and Markert (1994)
1.5 ug/g. The mean concentration of nickel in naturally occurring wetland macrophytes
was determined to be 8.94 ug/g, the mean concentration of nickel reported for freshwater
vascular plants is 6.2 ug/g (Outridge and Noller, 1991). As the only free-floating,
floating leaved life form included in this study, Lernna sp. accumulated higher
concentrations of nickel than any other species, which is contradictory to that reported by
Outridge and Noller (1991).
Selenium
The mean concentration of selenium observed in naturally occurring wetland
macrophytes in Arizona was 0.607 ug/g (Table 14). Lemna sp. accumulated the highest
concentrations of selenium, with a concentration range of 1.60-2.04 ug/g and a
concentration mean of 1.82 ug/g (Table 27). Fraxinus velutina also accumulated
selenium, a range of <0.8-2.60 ug/g was determined with a concentration mean of 1.50
ug/g. Selenium was detected in leaf tissues of the tree species Populus fremontii and
Salix gooddingii, with mean concentrations of 0.914 ug/g and 0.681 ug/g respectively,
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while no selenium was detected in the tissues of the shrub Salix lasiolepis. The
emergent species Scirpus americanus concentrated selenium to a greater degree in its root
tissues than shoots, with concentration means of 0.937 ug/g and 0.498 ug/g respectively.
Selenium was not detected in the emergent species Scirpus acutus or in the roots of
Typha domingensis. Selenium was also not detected in samples of the terrestrial herb,
Anemopsis californica.
Selenium concentrations in water samples were all below the minimum detection
limit, 25.0 ug/L (Table 16). EPA has established a drinking water MCL of 50.0 ug/L for
selenium, although no surface water CMC is suggested (EPA, 1998).
In soil samples, selenium was determined in a range from <2.5-10.3 ug/g, with most
samples being below the minimum detection limit (Table 17). Sites that had detectable
selenium concentrations include Patagonia-Sonoita Creek Preserve, St. David Cienega
and Bingham Cienega. Elevated selenium levels in the water at Patagonia-Sonoita Creek
Preserve correlated with maximum selenium concentrations in the tissues of Scirpus
americanus from the same site.
The mean concentration of selenium determined in naturally occurring wetland
macrophytes was 0.607 ug/g, while Outridge and Noller report a concentration mean of
1.1 ug/g for selenium in freshwater vascular plants in uncontaminated areas. In this
study, all of the species analyzed fell within the range reported by Kabata-Pendias and
Pendias (1992) for selenium in terrestrial plants, 0.01-2 ug/g. Markert (1994) reports a
selenium concentration of 0.02 ug/g for plants in general, which may represent the 89
80
percent of samples in this study that had selenium concentrations below the detection
limit.
Zinc
The mean concentration of zinc observed in naturally occurring wetland macrophytes
in Arizona was 26.1 ug/g (Table 14). Lemna sp. had the highest mean concentration of
zinc, with a range of 68.4-212 ug/g and a mean of 140 ug/g (Table 28). Tree species
Populus fremontii and Salix gooddingii were determined to have high levels of zinc in
leaf tissues, with concentration means of 46.1 ug/g and 45.5 ug/g respectively, Fraxinus
velutina accumulated the least of the tree species, with a mean of 8.18 ug/g. The shrub
Salix lasiolepis had a mean zinc concentration of 28.3 ug/g. Emergent species, Scirpus
acutus, Scirpus americanus and Typha domingensis, accumulated more zinc in roots than
in shoots, with mean concentrations of 21.0 ug/g and 8.19 ug/g for root and shoot tissues
respectively. Anemopsis californica was determined to have higher zinc concentrations
in leaf tissues than in roots, with means of 15.8 ug/g and 14.4 ug/g respectively.
Zinc concentrations in water samples were all below the minimum detection limit,
50.0 ug/L (Table 16). EPA has suggested a surface water CMC of 120 ug/L for the
protection of aquatic organisms (EPA, 1998). Zinc levels determined in natural wetland
samples for this study are with a permissible range.
In soil samples, zinc was determined in a range of 16.9-268 ug/g, with a mean
concentration of 97.2 ug/g (Table 17). The highest zinc concentrations in soil samples
81
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were from Patagonia-Sonoita Creek Preserve, although there was not a significant
increases in plant tissue concentrations of zinc from this site.
Zinc concentrations determined in the tissues of Anemopsis californica, Fraxinus
velutina and Scirpus acutus were below the reported range for crops and terrestrial plants,
27-150 ug/g (Kabata-Pendias and Pendias, 1992; Markert, 1994). The mean
concentration of zinc determined in naturally occurring wetland macrophytes was
26.1 ug/g, less than half that reported for freshwater vascular plants, 66 ug/g (Outridge
and Noller, 1991). Lemna sp. accumulated concentrations of zinc that are considered to
be excessive or toxic (Kabata-Pendias and Pendias, 1992).
Zinc concentrations determined in naturally occurring samples of tree species
Fraxinus sp., Populus fremontii and Salix sp. were less than those reported by Karpiscak
et al. (1997, 1998) for the same species in potable-fed constructed wetland systems, and
greater than those reported for effluent-fed constructed wetland systems (Figure 7).
Anemopsis californica roots, Scirpus americanus roots and shoots, and Typha
domingensis roots and shoots all had lower zinc concentrations than those reported in
constructed wetland systems (Karpiscak et al., 1997, 1998).
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84
CHAPTER 5: CONCLUSIONS
Lemna sp. was found to accumulate greater concentrations of the elements arsenic,
cadmium, chromium, cobalt, copper, lead, manganese, nickel, selenium and zinc than any
other naturally occurring wetland macrophyte in this study. Lemna sp. was especially
efficient at concentrating manganese and nickel, having concentration means more than
10 times those of other species analyzed. In this study Lemna sp. was represented by
only two samples, although separate studies have observed elevated concentrations of
nutrients and heavy metals in species of Lemna (Sharma and Guar, 1995).
Anemopsis californica accumulated the highest mean concentration of aluminum in
this study, and was second to Lemna sp. in accumulating the elements chromium, cobalt
and copper. Scirpus americanus accumulated the highest mean concentration of iron in
its root tissues, and the second highest concentrations of aluminum, arsenic, lead and
nickel.
Leaves of the tree and shrub species Fraxinus velutina, Populus fremontii, Salix
gooddingii and Salix lasiolepis generally had the lowest concentrations of nutrients and
heavy metals, with a few unusual exceptions. Salix gooddingii accumulated high
concentrations of manganese in its leaf tissues, second only to Lemna sp. Elevated
concentrations of nickel and zinc were observed in the leaf tissues of Populus fremontii
and Salix gooddingii, again only second to concentrations found in Lemna sp. Selenium
was accumulated in the leaf tissues of Fraxinus velutina, almost three times higher than
the concentration mean for all wetland macrophytes.
85
Root tissues of naturally occurring wetland macrophytes accumulated greater
concentrations of aluminum, copper, iron and zinc than shoot and leave tissues in all
species studied. Additionally, roots of the emergent species Scirpus americanus, Scirpus
acutus and Typha domingensis accumulated greater concentrations of arsenic, chromium
and cobalt than did the shoots of these emergent species. Typha domingensis was found
to concentrate the elements cadmium, lead, nickel and selenium to a greater extent in its
shoot tissues than roots, while Scirpus acutus and Scirpus americanus allocated these
heavy metals to their root tissues. Anemopsis californica had higher concentrations of
chromium, cobalt, manganese and nickel in its leaf tissues. Emergent species had greater
manganese concentrations in shoots than in roots, with Scirpus acutus accumulating an
unusually high manganese concentration in its shoot tissues. Macrophytic species that
transfer metals into leaf and shoot tissues, such as Typha domingensis and Anemopsis
californica, should be preferentially planted in constructed wetland systems that use
harvesting practices for contaminant removal. Alternately, metal translocation is
considered undesirable from an ecotoxicological standpoint, as accumulated metals could
easily pass into the food chain through herbivorous and detritus feeders (Ye et al.,
1997b). Macrophytic species which allocate metals in their root tissues, or those which
do not concentrate metals at all, should be used in constructed wetlands that serve as a
habitat for wildlife.
Naturally occurring wetland macrophytes were determined to have mean
concentrations of copper, lead and zinc within the same range as those reported by
Karpiscak et al. (1997, 1998) for wetland macrophytes grown in potable and effluent-fed
86
constructed wetland systems, as summarized in Table 29. The mean concentration of
manganese determined in naturally occurring wetland macrophytes was greater than the
range of manganese reported for macrophytes grown in potable-fed constructed wetlands,
although within that reported for effluent-fed constructed wetland macrophytes
(Karpiscak et al., 1997, 1998). Mean iron concentrations determined in naturally
occurring wetland macrophytes were greater than the ranges reported for iron in potable
and effluent-fed constructed wetland plants (Karpiscak et al., 1997, 1998).
Concentrations of nutrients and heavy metals reported by Outridge and Noller (1991)
in freshwater vascular plants from uncontaminated environments were all greater than
those determined for naturally occurring wetland macrophytes, with the exception of
manganese and nickel (Table 29). Naturally occurring wetland macrophytes generally
fell within the ranges reported as normal for nutrient and heavy metal concentrations in
terrestrial plants, with the exception of manganese and nickel, which had higher
concentrations than those reported for terrestrial plants, as summarized in Table 29
(Kabata-Pendias and Pendias, 1992; Markert, 1994).
Maximum nutrient and heavy metal concentrations reported for wetland macrophytes
from contaminated and uncontaminated environments (Vymazal, 1995) were two to five
orders of magnitude higher than levels which were determined to be naturally occurring
(Table 29).
Mean concentrations of elements in the tissues of macrophytes from natural wetlands
were similar to those reported for potable and effluent-fed constructed wetland systems,
•0
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although concentrations reported for macrophytes from contaminated wetlands were two
to five orders of magnitude greater than those determined to be naturally occurring.
89
APPENDIX A: EMPIRE CIENEGA
90
91
APPENDIX B: CANELO HILLS CIENEGA
92
93
APPENDIX C: PATAGONIA-SONOITA CREEK PRESERVE
94
95
APPENDIX D: ST. DAVID CIENEGA
96
97
APPENDIX E: AGUA CALIENTE PARK
98
99
APPENDIX F: COOK'S LAKE
100
1 01
APPENDIX G: BINGHAM CIENEGA
102
103
APPENDIX H: COMPLETE PLANT DATA BY STUDY SITE
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REFERENCES
Albers, P.H., and M.B. Camardese. 1993a. Effects of acidification on metal accumulation
by aquatic plants and invertebrates. 1. constructed wetlands. Environmental
Toxicology and Chemistry 12:959-967.
Albers, P.H., and M.B. Camardese. 1993b. Effects of acidification on metal accumulation
by aquatic plants and invertebrates. 2. wetlands, ponds and small lakes.
Environmental Toxicology and Chemistry 12:969-976.
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