Metal Loadings to the Hudson River
and New York Harbor: How have
they changed?
Robert Mason
Department of Marine Sciences
University of Connecticut, Groton, CT 06340
Mostly based on data collected and analyzed
during a project funded by the Hudson River
Foundation (Fitzgerald and Mason as PI’s)
Outline
• Why we care about metals in the Hudson?
• Sediment Data
• Water Data – Factors controlling distributions
in the upper estuary and NY/NJ Harbor
• Water Data – Changes over time
• Mass Balances for the Metals - Sources to
the Harbor, and major sinks
Levington et al 2008
Metal Toxicity?
1) Impact is on lower food chain
organisms for most metals as
bioaccumulation is greatest
for plankton. In the Hudson,
Cd is the most important example
as there are known point source
contamination (e.g. Foundry Cove)
that been shown to cause toxicity.
However, organisms were able to
generate resistance to the Cd.
2) Toxicity of highly bioaccumlative compounds is manifest in the higher level
consumers and toxicity to plankton may not occur. Example is methylmercury
which has most impact for higher food chain consumers (humans, mammals
and birds) that feed on piscivorous fish
EPA
A number of species exceed the EPA recommended value for mercury
(assuming all as methylmercury)
Health of the Harbor report
Gobeille et al., 2006
People consuming local fish have higher mercury levels than those who do
not .
Levels found in Hudson River similar to that for other ecosystems where
people eat local fish
Levels below the EPA suggested reference level of 5.8 ng/mL.
Gobeille et al., 2006
Sediment Concentrations
Levels of metals in
sediments of the Hudson
River are elevated above
other US estuaries and
higher than background
concentrations
Taken from Bopp et al., Ch 24
Changes in Sediment Metal Conc (ppm) between 1960’s & 1990’s
Metal
Pb mid-60’s
Pb 1990’s
%Decrease
Cd mid-60’s
Cd 1990’s
%Decrease
Cu mid-60’s
Cu 1990’s
%Decrease
Zn mid-60’s
Zn 1990’s
%Decrease
Cr mid-60’s
Cr 1990’s
%Decrease
Hg mid-60’s
Hg 1990’s
%Decrease
NY/NJ
Harbor
235
126
46
5.6
1.1
80
268
122
54
352
232
34
286
116
59
3.4
1.6
53
Jamaica Arthur
Bay
Kill
336
81
76
10.9
1.7
84
362
93
74
608
210
65
225
102
55
2.3
0.45
80
398
211
47
21.3
2.9
86
1395
312
78
1045
404
61
325
166
49
20
4.94
75
Newark Hacken- Passaic
Bay
sack R R
373
142
62
11
1.95
82
342
160
53
717
265
63
343
109
68
8.1
3
63
240
132
45
741
327
56
968
568
307
46
12.4
4.2
66
248
120
52
1052
523
50
10.8
3.6
67
7.77
3.64
53
12.48
1.83
85
Changes in Sediment Metal Conc (ppm) between 1960’s & 1990’s
Metal
Pb mid-60’s
Pb 1990’s
%Decrease
Cd mid-60’s
Cd 1990’s
%Decrease
Cu mid-60’s
Cu 1990’s
%Decrease
Zn mid-60’s
Zn 1990’s
%Decrease
Cr mid-60’s
Cr 1990’s
%Decrease
Hg mid-60’s
Hg 1990’s
%Decrease
Main,
Batten Main,
above Dam Kill
Lock 2
Mohawk Main at Main, at
River
Troy
Kingston
1560
69
96
46
45
2
512
42
92
68
9.1
87
411
42
90
118
44
63
115.0
5.7
22.4
0.5
10.6
3.4
30
74
121
0.6
89
42
<0.5
>98
31
1.2
Increase
132
2.6
75
508
0.03
99
76
31
74
1100
108
90
1440
154
89
8.93
0.56
94
30
29
1026
265
74
26
21
19
22
29
662
79
88
-
43
67
103
59
88
1056
224
79
27
64
308
127
59
195
74
62
0.93
0.19
80
0.2
52
0.45
0.13
71
1.95
0.42
78
From Bopp
et al., Ch 24
Sediment Concentration
Changes
• For most metals and locations, there has been a
dramatic decrease in concentration between
1960’s and 1990’s
• In mainstem, no trend in concentration with
distance
• Changes somewhat less dramatic in the lower
estuary
• Concentrations still elevated above background
for many metals.
• How does this impact the ecosystem?
Levinton & Pochron,
2008
Metal
Main,
Batten
above Dam Kill
Main, Mohawk Main at Main, at Relative change in fish
Lock 2 River
Troy
Kingston concentration less
HRM ~195
HMR ~165
Hg mid-60’s
8.93
Hg 1990’s
0.56
%Decrease
94
0.2
HRM 150 HRM ~90
0.45
1.95
0.93
0.13
0.42
0.19
71
78
80
than that of sediment
for Hg. Also fish do not
track sediment
concentration
Assessment of Water Column Data
Sources of Data

Data summarized was derived from a variety of literature sources
and databases. Evaluated for appropriateness of the analytical
methods and complete presentation of quality assurance/quality
control (QA/QC) procedures and results.

Large databases included CARP (Contaminant Assessment and
Reduction Project), EMAP (Environmental Monitoring and
Assessment Project), and data from regulatory agencies (e.g.,
NYSDEC State Waters Monitoring Section [SWMS] and Division of
Water).

Most published studies have reported surface and deep water
concentrations of metals (Hg, Cd, Cu, Fe, Ni, Zn, Ag, and Pb) in
the lower Hudson (south of Newburg; ~25 to 100 km north of the
Battery) and the estuarine turbidity maximum (ETM; south of the
Harlem River; ~ 4 to 25 km).
Hudson River Estuary
Waterford
••Cohoes
• Glenmont
Hudson
River
Watershed
0
Metal
Ni
Cu
Zn
Cd
Hg
Pb
Atomic
Mass
1 ug/L = x nM
1ppm = x nmol/g
58.7
63.5
65.4
112.4
200.6
207.2
• Kingston-Poughkeepsie
10 20 30 Km
NY/NJ Harbor
17.0
15.7
15.3
8.9
5.0
4.8
Water - Middle & Upper Hudson
70
60
50
40
30
20
10
0
50
90
total
dissolved
% particulate
80
70
60
40
50
30
40
20
30
20
10
0
t
s
d
ie
on
oe
for
ps
h
r
m
e
e
o
t
en
ke
C
Gl
Wa
gh
u
Po
10
0
90
80
160
140
120
100
80
60
40
20
0
70
400
100
60
50
40
30
20
10
0
Zn 1993-2006
300
Zn (nM)
Ni (nM)
60
Ni 1993-2006
100
100
particulate fraction (%)
80
Cu 1993-2006
TSS
90
80
70
60
200
50
40
100
30
20
10
0
t
s
d
ie
on
oe
for
ps
h
r
m
e
e
o
t
en
ke
C
Gl
Wa
gh
u
Po
0
TSS (mg l-1)
90
80
70
100
400
350
300
250
200
Cu (nM)
Pb 1993-2006
particulate fraction (%)
140
120
100
80
60
40
20
12
10
8
6
4
2
0
particulate fraction (%)
Pb (nM)
(SWMS; collected 1993-2006; mean ± SD)
Water - Middle & Upper Hudson
(CARP; collected 1999-2001; mean ± SD)
total
dissolved
% particulate
90
150
80
100
70
50
60
14
12
10
8
6
4
2
0
50
.
s
d
sie
gh
or
oe
f
p
u
r
h
e
o
e
Co
-P
ate
hk
n
W
g
o
u
st
Po
ng
i
K
40
30
20
10
0
2.00
Cd 1999-2001
100
90
1.50
80
1.00
70
0.25
60
0.20
50
40
0.15
30
0.10
20
0.05
10
0.00
0
h.
s
d
ie
g
or
oe
f
ps
u
r
h
e
o
e
Co
-P
ate
hk
n
W
g
o
u
st
Po
ng
i
K
particulate fraction (%)
Hg 1999-2001
Cd (nM)
Hg (pM)
200
2.50
100
particulate fraction (%)
250
TSS - Upper Hudson/Sources of Metals
(SWMS; collected 1993-2006; mean ± SE)
30
12
10
8
20
6
15
4
10
2
5
2
0
0
0
25
8
30
6
20
4
20
15
6
10
4
2
0
t
s
d
ie
on
oe
for
ps
h
r
m
e
e
o
e
t
en
C
hk
Gl
Wa
ug
o
P
250
Zn 1993-2006
5
0
Zn (µmol g-1)
suspended particle
metal/ Fe
0
25
Ni/Fe (x 10-4)
Ni (µmol g-1)
8
suspended particle
concentration
10
30
Ni 1993-2006
10
40
Cu/Fe (x 10-4)
25
Cu (µmol g-1)
10
12
50
Cu 1993-2006
Pb/Fe (x 10-4)
Pb (µmol g-1)
Pb 1993-2006
200
20
150
15
100
10
5
0
t
s
d
ie
on
oe
for
ps
h
r
m
e
e
o
e
t
en
C
hk
Gl
Wa
ug
o
P
50
0
Zn/Fe (x 10-4)
12
TSS - Upper Hudson Sources of Hg
(CARP & SWMS; collected 1999-2001; mean ± SE)
200
200
(suspended particle Hg:Fe ratios)
(suspended particle concentrations)
180
180
160
Total Hg (pM)
Total Hg (pM)
160
Poughkeepsie (2.1)
140
120
100
Cohoes (10.2)
80
120
100
-6
Cohoes (11.6 x 10 )
80
Waterford (6.8)
60
-6
Poughkeepsie (3.0 x 10 )
140
-6
Waterford (9.2 x 10 )
60
40
40
0
10
20
30
40
50
TSS (mg L-1)
60
70
80
0
10
20
30
40
total Fe (µM)
50
60
Spatial/seasonal MMHg distributions
(CARP; collected 1999-2000; mean ± SE)
0.6
2.2
3
0.3
2
0.2
Filtered MMHg (pM)
Filtered MMHg (pM)
4
0.4
spring 1999
fall 1999
spring 2000
summer 2000
2.0
diss. MMHg/HgT (%)
MMHg
diss. MMHg/HgT
0.5
5
0.5
Waterford
0.4
ETM
0.3
0.2
1
0.1
0.1
0.0
0
.
rd
on
sie
ep
ds
r fo
ep
ke
u
e
e
h
t
k
H
g
Wa
gh
er
ou
u
P
w
o
n
P
Lo
sto
g
n
Ki
M
ET
0.0
0
50
100
150
Distance (km)
200
250
Summary
middle and upper Hudson

Average total (filtered + particulate) concentrations of Hg (58 to
130 pM), Cu, Ni, Zn, and total suspended solids (TSS) in surface
waters are highest at Poughkeepsie.

Cd (0.97 to 1.3 nM) and Pb were more uniformly distributed in the
middle and upper Hudson.

Fe-normalized suspended particle concentrations of Hg, Cd, Pb,
Cu, Ni, and Zn were elevated in the upper Hudson at Waterford
and Cohoes as compared to Poughkeepsie, indicating watershed
sources of trace metals.

MMHg in the middle and upper Hudson is likely derived/connected
to net production in the Hudson River watershed.
Hudson River - Water
(Lower Hudson and ETM)
(CARP; collected 1999-2001; mean ± SE)
2.2
2.0
1.8
1.6
1.4
1.2
200
total HgT
filtered HgT
180
160
140
1.0
Cd (nM)
120
Hg (pM)
total Cd
filtered Cd
100
80
60
0.8
0.6
0.4
40
0.2
20
0
ie
p.
on
ord
ee
ps
ds
k
e
erf
u
e
h
t
k
H
g
a
h
r
u
W
ug
we
-Po
n
Po
Lo
o
t
gs
Kin
M
ET
0.0
.
n
rd
sie
ep
so
e
p
rfo
d
k
e
e
u
e
h
t
k
h
rH
ug
Wa
ug
we
-Po
n
Po
Lo
to
gs
n
i
K
M
ET
Summary
Lower Hudson and ETM

In the estuarine turbidity maximum (ETM), average total Cd
concentrations (0.74 to 1.2 nM, surface waters) are similar to the
middle and upper Hudson sites, while average total Hg (54 to 1110
pM, surface and bottom waters) is elevated as compared to the
rest of the upper Hudson.

The filtered fraction of Cd increases dramatically with salinity (83 to
120% of total Cd) in the lower Hudson River, and higher total Hg
and Cd levels are associated with spring high flow periods.

Average surface water suspended particle concentrations of Hg
(2.20 to 3.54 nmol g-1) and Cd (5.45 to 12.6 nmol g-1) are largely
overlapping between the ETM and lower Hudson.

ETM and upper Hudson suspended particle metals concentrations
are elevated as compared to the middle Hudson (Poughkeepsie),
indicating sources of metals in both regions.
Major Rivers – NY/NJ Harbor
180
25
20
Hg (pM)
160
140
15
120
100
80
10
60
40
5
20
0
l
.
t
t
rf
rf
al
uth -tida
tR
su n-bo
su h-bo -tid
s
o
a
n
h
. m id
ita
ta
ut mid
ut
rE
ck . m
ari Rar
mo . mo ss.
we
R
.
o
Ha ack
L
ss ss Pa
H
Pa Pa
0
2.0
1.8
1.6
1.4
70
total Cd
filtered Cd
suspended particle
Cd
1.2
60
50
40
1.0
0.8
0.6
30
20
0.4
0.2
0.0
t
rf
rf
al
al
ot
th
R.
st
ou d-tid
-su an-b
-su th-bo d-tid
a
n
h
m
t
i
i
E
a
t
.
r
rit Rari
ou ou . m
ck . m
we
Ra
. m s. m ass
o
Ha ack
s
L
s
s
P
H
Pa Pa
10
0
suspended particle Cd (nmol g-1)
30
total HgT
filtered HgT
suspended particle
Hg
Cd (nM)
1200
1000
800
600
400
suspended particle Hg (nmol g-1)
(CARP; mean ± SE; collected 1999-2001)
Summary - Rivers

Average total Hg (145 and 433 pM, surface and bottom waters)
and Cd (0.97 and 1.35 nM) concentrations at the mouth of the
Passaic River were elevated as compared to the Hudson ETM,
while only total Hg (109 pM) was elevated at the mouth of the
Hackensack River.

Concentrations in the lower East River and the Raritan River were
similar to levels in the Hudson ETM.

Average suspended particle Hg (9.8 to 20.8 nmol g-1) and Cd (9.6
to 49.2 nmol g-1) concentrations were elevated in both the
Hackensack and Passaic as compared to the Hudson, although
suspended particle Cd was less near the mouths of rivers.
NY/NJ Harbor - Water
(CARP; collected 1999-2001; mean ± SD)
1.0
Hg (pM)
60
60
40
20
0
ay rbor Bay rbor Bay ight
B
B
a
a
ark er H ritan er H aica NY
w
Ra Low Jam
Ne Upp
40
20
0
total
filtered
% particulate
TSS
0.8
80
60
0.6
40
0.4
0.2
0.0
ay rbor Bay rbor Bay ight
B
B
a
a
ark er H ritan er H aica NY
w
Ra Low Jam
Ne Upp
50
100
40
30
20
20
10
0
0
TSS (mg l -1)
80
Cd
particulate (%)
1.2
Cd (nM)
Hg
100
particulate (%)
400
300
200
100
NY/NJ Harbor Water
(Balcom et al. 2008; collected 2002-2003; mean ± SD)
total
filtered
% particulate
TSS
MMHg (pM)
1.2
1.0
80
60
0.8
0.6
0.4
40
ay rbor Bay rbor Bay ight
B
rk r Ha itan r Ha aica Y B
a
N
r
w
e
e
Ra Low Jam
Ne Upp
170
160
40
30
20
20
10
0
0
0.2
0.0
180
100
TSS (mg l -1)
MMHg
particulate (%)
2.2
2.0
1.8
NY/NJ Harbor - Water
40
0.5
20
0.0
0
25
60
20
40
15
10
20
5
total
filtered
% particulate
25
60
20
15
10
40
20
5
0
r
r
k
y
y
y
Ba rbo Ba rbo Ba oo
rk r Ha itan r Ha aica dy H
a
r
w
e
e
Ra Low Jam -San
Ne Upp
y
wa
ka
c
Ro
50
100
80
0
45
14
Zn
TSS
40
35
10
30
8
25
20
6
15
4
10
5
0
12
0
r
r
k
y
y
y
oo
Ba rbo Ba rbo Ba
rk r Ha itan r Ha aica dy H
a
r
w
e
e
Ra Low Jam -San
Ne Upp
y
wa
ka
c
Ro
2
0
TSS (mg L-1)
Ni
0
Zn (nM)
40
30
80
particulate (%)
60
100
Cu
30
Cu (nM)
80
particulate (%)
35
1.0
35
40
100
Pb
particulate (%)
40.0
35.0
30.0
25.0
20.0
15.0
10.0
5.0
Ni (nM)
Pb (nM)
(Paulson, 2005; collected 1999; mean ± SD)
Concentration (nM)
Temporal Comparison Water
450
400
350
300
250
200
150
100
50
1974/1975
1999
Filtered Metals
Klinkhammer and Bender (1981)
collected 1974-1975
NY Bight
Paulson (2005)
collected 1999
Rockaway-Sandy Hook
transect
14
12
10
8
6
4
2
0
Cd
Concentration (nM)
(mean ± SD)
450
400
350
300
250
200
150
100
50
Cu
1974/1975
1999
Ni
Zn
Total Metals
Sañudo-Wilhelmy and Gill (1999)
reported a similar decrease in
dissolved metals for the Hudson
ETM and Lower Harbor between
1974/1975 and 1995/1997.
16
14
12
10
8
6
4
2
0
Cd
Cu
Ni
Metal
Zn
NY/NJ Harbor – Recent Sediment
(CARP, collected 1999-2001;
EMAP, surface sediment collected 1998; mean ± SD)
40
35
30
18
16
14
12
10
8
6
4
2
0
Hg
ay rbor Bay rbor Bay ight
B
rk r Ha itan r Ha aica Y B
a
N
r
w
e
e
Ra Low Jam
Ne Upp
Cd (nmol g-1)
Hg (nmol g-1)
suspended particles
sediment
sediment
50
45
40
35
30
25
Cd
20
15
10
5
0
ay rbor Bay rbor Bay ight
B
rk r Ha itan r Ha aica Y B
a
N
r
w
e
e
Ra Low Jam
Ne Upp
Circles are data not included in the averages as considered outliers
NY/NJ Harbor - Recent Sediment
(Balcom et al., 2008 and Hammerschmidt et al., 2008
suspended particles and surface sediment collected 2002-2003; mean ± SD)
suspended particle
sediment
suspended particle
MMHg (pmol g -1)
sediment
60
55
50
45
40
35
30
25
20
15
10
5
0
MMHg
ay rbor Bay rbor Bay ight
B
B
a
a
ark er H ritan er H aica NY
w
Ra Low Jam
Ne Upp
Circles - data not included in the averages
NY/NJ Harbor – Recent Sediment
(Paulson, 2005, suspended particles collected 1999;
EMAP, surface sediment collected 1998 and 1993-1994; mean ± SD)
suspended particles
sediment
sediment
suspended particles
5
10
Pb
9
Cu (µmol g -1)
Pb (µmol g-1)
4
3
2
3
2
1
0
0
1.6
10
Ni
Zn
8
Zn (umol g-1)
1.4
Ni (µmol g-1)
8
4
1
1.8
Cu
1.2
1.0
0.8
0.6
0.4
6
4
2
0.2
0.0
0
t
r
r
k
y
y
y
Ba arbo n Ba arbo a Ba Hoo Bigh
k
r
H rita r H aic dy NY
wa er
e
n
Ne Upp Ra Low Jam -Sa
y
a
aw
ck
Ro
t
r
r
k
y
y
y
Ba arbo n Ba arbo a Ba Hoo Bigh
k
r
H rita r H aic dy NY
wa er
e
n
Ne Upp Ra Low Jam -Sa
y
a
aw
ck
Ro
Circles - data not included in the averages
ETM and NY/NJ Harbor - Ratios
(Paulson, 2005 and Feng et al., 2002 - suspended particles collected 1994-1999 ;
EMAP, surface sediment collected 1998 and 1993-1994; mean ± SE)
70
70
Cu
Pb
Cu/Fe and Cu/Al (x 10 -4)
Pb/Fe and Pb/Al (x 10 -4)
80
60
50
40
30
20
10
60
50
40
30
20
10
0
0
25
250
20
15
10
5
0
)
)
ht
or
or
ay
ok
km
km
Ho
Big
arb
arb
nB
a
H
H
y
(10
(4
Y
t
r
r
N
ri
nd
M
M
pe
we
Ra
Sa
ET
ET
Up
Lo
k.c
Ro
Zn/Fe and Zn/Al (x 10 -4)
Ni/Fe and Ni/Al (x 10 -4)
Ni
200
suspended particle metal/Fe
sediment metal/Fe
suspended particle metal/Al
sediment metal/Al
Zn
150
100
50
0
)
)
ht
or
or
ay
ok
km
km
Ho
Big
arb
arb
nB
a
H
H
y
(10
(4
Y
t
r
r
N
ri
nd
M
M
pe
we
Ra
Sa
ET
ET
Up
Lo
k.c
Ro
ETM and NY/NJ Harbor - Ratios
(Paulson, 2005 and Feng et al., 2002 - suspended particles collected 1994-1999 ;
EMAP, surface sediment collected 1998; mean ± SE)
suspended particle metal/Fe
sediment metal/Fe
suspended particle metal/Al
sediment metal/Al
water POC
sediment siltclay
sediment TOC
80
0.20
60
0.15
40
0.10
0.05
0.00
)
r
)
ht
or
ay
ok
km
rbo
km
Ho
Big
arb
nB
Ha
H
a
y
(10
(4
Y
t
i
r
r
d
N
r
n
M
M
pe
we
Ra
Sa
ET
ET
Up
Lo
k.c
Ro
20
0
0.50
0.45
2000
1500
1000
500
Cd/Fe and Cd/Al (x 10 -4)
Hg/Fe and Hg/Al (x 10-4)
0.25
2500
TOC (µmol g-1)
100
Hg
POC (µM) and siltclay (%)
0.30
Cd
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0
0.00
)
r
)
ht
or
ay
ok
km
rbo
km
Ho
Big
arb
nB
Ha
H
a
y
(10
(4
Y
t
i
r
r
d
N
r
n
M
M
pe
we
Ra
Sa
ET
ET
Up
Lo
k.c
Ro
Summary – NY/NJ Harbor

Regional average trace metal concentrations of Hg (3.2 to 166
pM) and Cd (0.19 to 0.90 nM) in NY/NJ Harbor were generally
elevated and more variable near the input of major rivers in
Newark Bay and the Upper Harbor, roughly corresponding with
elevated TSS levels.

Harbor Hg and Pb were mainly in the particulate phase, while
Cd, Cu, and Ni have more metal in the dissolved fraction at
elevated Harbor salinities.

Over 25 years (1974 to 1999), average dissolved metals
concentrations (surface and deep) in the Lower Harbor and NY
Bight region were reduced by 85 to 90%.
Summary – NY/NJ Harbor
(continued)

There was good agreement between average suspended
particle concentrations of Hg (1.1 to 8.7 nmol g-1), Cd (3.1 to
13.2 nmol g-1), and other metals with surface sediment
concentrations in the Harbor, while suspended particle
concentrations in the ETM are known to be elevated as
compared to sediments (Feng et al., 2002).

However, Al- and Fe-normalized suspended particle metal
concentrations were reduced in the Hudson ETM and elevated
in Raritan Bay and at the Rockaway-Sandy Hook transect
suggesting metals enrichment due to association with fine
particulate material or particulate organic matter.
Budget sources – percent inputs
(mean ± SE)
Hg - 3100 moles y-1
69±27%
2±4%
2±0.2%
23±7%
5±0.5%
Rivers
East River
WPCFs
Atm. Deposition
Benthic flux
Cd - 25 K moles y-1
MMHg - 14 moles y-1
59±24%
57±26%
4±15%
26±3%
4±1%
9±1%
8±1%
21±11%
10±1%
2±0.3%
Budget sources – percent inputs
(mean ± SE)
Pb - 850 K moles y-1
Ni - 1700 K moles y-1
38±21%
88±8%
0.1±0.1%
4±1%
25±4%
6±0.1%
19±27%
16±0.4%
1±1%
2±0.2%
Cu - 2800 K moles
y-1
Zn - 7100 K moles y-1
60±23%
39±9%
6±2%
11±2%
21±0.5%
19±2%
11±28%
2±0.3%
23±0.4%
Rivers
East River
WPCFs
Atm. Deposition
Benthic flux
8%
Temporal Comparison of Metal Inputs
(mean ± SE or range)
Reference
Sampling
Period
Cd
(K moles y-1)
Ni
(K moles y-1)
Cu
(K moles y1)
Zn
(K moles y-1)
This Study
~ 2000 - 2006
25 ± 7.4
1700 ± 580
2800 ± 660
7100 ± 2100
Klinkhammer &
Bender (1981)
April 1974
280 - 590
4500 - 9500
5200 10000
11100 28300
(enhancement)
(11 to 24 x)
(2.5 to 5.5 x)
(2 to 3.5 x)
(1.5 to 4 x)
October 1975
190 - 500
3400 - 7500
4000 - 8400
7000 - 15100
(enhancement)
(8 to 20 x)
(2 to 4.5 x)
(1.5 to 3 x)
(1 to 2 x)
Decrease most dramatic for Cd - >90% reduction in inputs.
Other metals show more modest reductions over time.
Summary – Mass Balances

Current annual loadings (~2000 to 2006) to NY/NJ Harbor estimated
for Hg (3100 mol y-1), MMHg (37 mol y-1), Cd (25 Kmol y-1), Pb (850
Kmol y-1), Ni (1700 Kmol y-1), Cu (2800 Kmol y-1), Zn (7100 Kmol y-1)

The majority of inputs are from rivers (38 to 88% of totals).

River fluxes of metals were estimated independently using a Hudson
sediment delivery flux (8.12 ± 3.25 x 1011 g y-1; Wall et al. [2008] and
HydroQual [2003]) and mean suspended particle metals concentrations in the middle/lower Hudson. These estimates agreed well
with the annual loadings shown above.

Total inputs are significantly decreased for Cd (8 to 42x), Ni (2 to
5.5x), Cu (1.5 to 3.5x), and Zn (1 to 4x) since the mid 1970s (25 to 30
years).

The relative contribution of metals from sewage has decreased.

Hg inputs are likely to have declined by about a factor of 3-5 since
the mid-1960s.
Conclusions

There is a need for high quality time series measurements of
filtered and suspended particle metals concentrations, as well as
important ancillary parameters (e.g., POC), in the waters of the
Hudson River and NY/NJ Harbor.

The decline in metals concentrations in the waters of NY/NJ
Harbor since the mid-1970s was established by a comparison
between adjacent regions. The time series of measurements is
incomplete for any one region of the Harbor.

Limited measurements (1999-2001) of Hg and Cd concentrations
in the middle and upper Hudson, major regions of the Harbor, and
the East River, with almost no data on suspended particle
concentrations.
Conclusions
(continued)

The sediment-water fluxes of most trace metals has not been
measured in NY/NJ Harbor, and are needed considering the
importance of this source term in some mass balances (e.g.,
MMHg)

Bulk (wet and dry) atmospheric deposition measurements are
limited for most metals in the Harbor region, and are important to
mass balances since atmospheric deposition of metals and
subsequent yield from watersheds accounts for a substantial
portion of the fluxes of metals in rivers.

We hypothesize that much of the MMHg in NY/NJ Harbor is likely
connected to net production in the Hudson River watershed, and
that there is limited MMHg input from river sediments.
Seasonal distributions of Hg
(CARP; collected 1999-2000; mean ± SE)
250
Total Hg (pM)
200
spring 1999
fall 1999
spring 2000
summer2000
150
100
Waterford
50
ETM
Filtered Hg
20
Filtered Hg (pM)
Total Hg
spring 1999
fall 1999
spring 2000
summer2000
15
10
5
Waterford
ETM
0
0
0
50
100
150
Distance (km)
200
250
0
50
100
150
Distance (km)
200
250
Mass balances - NY/NJ Harbor
(mean ± SE; ~2000 to 2006)
Sources
Hg
(moles y-1)
MMHg
(moles y-1)
Cd
(K moles y-1)
Rivers
2100 ± 820
23 ± 9
14 ± 6.4
East River
700 ± 200
2.9 ± 0.5
6.5 ± 0.7
WPCF’s
140 ± 15
3.7 ± 0.4
2.1 ± 0.3
Atmospheric Deposition
60 ± 5
0.9 ± 0.1
1.1 ± 0.2
Benthic Flux
60 ± 130
8±4
1.1 ± 3.7
Total
3100 ± 900
37 ± 10
25 ± 7.4
(moles y-1)
(moles y-1)
(K mol y-1)
Estuarine Exchange
1300 ± 270
14 ± 2.0
18 ± 2.4
Evasion
60 ± 20
--
--
Sediment Burial
1700 ± 9001
4.0 ± 3.0
6.7 ± 8.01
(Photo)demethylation
--
2.0 ± 1.0
--
Biological Processes
--
17 ± 111
--
Total
3100
37
25
Sinks
1 closing
term
Watershed Contributions

Watershed Hg yields were estimated to range from 0.011 to 0.019
µmol m-2 y-1 (25-30% of atmospheric wet deposition) resulting in
delivery of 480 to 780 mol Hg y-1 to the major rivers surrounding
the Harbor (Balcom et al., 2008).

Watershed fluxes are estimated to account for 23 to 37% of the
Hg flux from rivers to NY/NJ Harbor (2100 ± 820 mol y-1)

Assuming that the watershed yield of MMHg is 3% of the HgT flux
(based on atmospheric deposition measurements), watershed
MMHg yields are estimated to range from 3.4 to 5.6 x 10-4 µmol
m-2 y-1 (Driscoll et al. [1998] reported 8.4 x 10-4 µmol m-2 y-1),
resulting in delivery of 14 to 23 mol y-1 to rivers.

Indicates that watershed delivery may account for the majority of
the MMHg flux from rivers to NY/NJ Harbor (23 ± 9 mol y-1)
estimated in the current study, and that there may be limited net
in-situ production and input of MMHg from river sediments.
Hg Accumulation in NY/NJ Harbor

The Pettaquamscutt River Estuary (PRE; RI) is relatively remote
from point sources with a watershed that can be characterized as
rural/residential.

Scrupulously dated, varved sediment core (Lima et al., 2003/2005)
provides a potentially valuable analog for assessing anthropogenic
impact and temporal changes in Hg accumulation/inputs in the
Harbor Estuary over the past half century.

Hg flux ratio (actual/preindustrial Hg accumulation) peaked in 1950
and 1960 at 12, but the ratio in 1997 was 4, representing a
substantial decline in Hg inputs by about a factor of 3.
Hg Accumulation in NY/NJ Harbor
(continued)

Sediment Hg accumulation fluxes are not available for the Harbor,
but using sediment Hg concentrations (Bopp et al., 2006),
approximate accumulation ratios can be estimated.

In the mid-1960s the actual/preindustrial Hg concentration ratio
ranged from 13 (Jamaica Bay) to >100 (Arthur Kill), and were
reduced to 3 to 27 in 1995/1996.

Therefore, there has been a decline in contaminant Hg inputs to
the Harbor Estuary since the 1960s, and although difficult to
provide a quantitative estimate, a factor of 3-5 is likely

Although there is substantially more Hg accumulating per unit
area, the Harbor is comparable to the PRE where the decline in Hg
accumulation was about 3.