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Environ Monit Assess (2016) 188:628

DOI 10.1007/s10661-016-5639-y

Heavy metal distribution and water quality characterization


of water bodies in Louisiana’s Lake Pontchartrain Basin, USA
Zengqiang Zhang & Jim J. Wang & Amjad Ali &
Ronald D. DeLaune

Received: 22 February 2016 / Accepted: 10 October 2016


# Springer International Publishing Switzerland 2016

Abstract The seasonal variation in physico-chemical higher concentrations in Amite River, Mississippi River,
properties, anions, and the heavy metal (Cd, Co, Cr, Cu, Industrial Canal, and Lacombe Bayou during summer. The
Mn, Ni, Pb, and Zn) concentration was evaluated in water Cr concentration was higher than WHO drinking water
from nine different rivers in Lake Pontchartrain Basin, standards, implicating water unsuitability for drinking pur-
Louisiana, USA. The water quality parameters were com- poses in all the rivers associated with the Lake
pared with toxicity reference values (TRV), US Environ- Pontchartrain Basin. Cu showed no pollution risk for the
mental Protection Agency (USEPA) drinking/aquatic life study area. Mn and Co were similar to concentration in
protection, and WHO standards. Among physico-chemical Lacombe Bayou, Liberty Bayou, Blind River, and Indus-
properties, pH, DO, and turbidity were high during spring, trial Canal. Mn levels were greater than WHO standards
while, EC, temperature, and DOC were high during sum- for the Tickfaw River, Tangipahoa River, and Blind River
mer and vice versa. The anion study revealed that the in both seasons. Blind River, Tangipahoa River, Tickfaw
concentrations of F−, Cl−, and NO3− were higher during River, and Amite River will require more monitoring for
summer and Br− and SO4− were higher during spring. Our determining possible Mn pollution. Ni content in river
research findings showed anion concentration decreased in water during both seasons showed low pollution risk.
the order of Cl− > SO4− > NO3− > Br− > F−, in accordance Liberty Bayou and Industrial Canal concentrations were
with the global mean anion concentration. The dissolved closer to the WHO regulatory standards, indicating possi-
heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb) except Zn were ble risk of Pb pollution in these water bodies. The Zn
higher during spring than summer. None of the rivers content was near the USEPA aquatic life standards in
showed any Cd pollution for both seasons. Co showed summer for all water bodies. None of the rivers showed
any risk associated with Cd, Co, Cu, and Ni levels but
medium to higher risk to aquatic life from Cr and Zn for
Z. Zhang (*) : A. Ali
College of Natural Resources and Environment, Northwest A&F
both seasons for most of the rivers. Metal fractionation
University, Taicheng Road 3#, Yangling, Shaanxi 712100, China revealed the decreasing order of inert > labile > organic.
e-mail: zhangzq58@126.com The high inert fraction in the rivers under study reflects the
major contribution of natural sources in Lake Pontchartrain
J. J. Wang (*)
Basin. The labile and organic forms of Cd, Cu, Ni, and Zn
School of Plant, Environmental, and Soil Sciences, Louisiana
State University AgCenter, Baton Rouge, LA 70803, USA pose potential higher risk to the aquatic life in the Lake
e-mail: JJWang@agcenter.lsu.edu Pontchartrain Basin.
R. D. DeLaune
Department of Oceanography and Coastal Sciences, School of
Coast and Environment, Louisiana State University, Baton Rouge, Keywords Heavy metals . Anions . Water quality . Lake
LA 70803-7511, USA Pontchartrain
628 Page 2 of 14 Environ Monit Assess (2016) 188:628

Introduction introduction in food chain (Larocque and Rasmussen


1998; Meador 2006).
In recent years, heavy metal introduction to water bodies Chemical, toxicological, and ecological approaches
has attracted global concern due to environmental risk, have been used extensively in assessing impacts of
high loads, and persistent nature (Islam et al. 2015; metals pollution in aquatic environments. To evaluate
Dhanakumar et al. 2015). Large quantities of hazardous the quality of the aquatic systems, toxic metals can be
chemicals including heavy metals are released into determined in water, to confirm the source of toxicants.
streams or water bodies due to rapid population growth Although most metals are naturally occurring through
and intensive domestic activities, as well as expanding biogeochemical cycles (Garrett 2000), they may also
industrial and agricultural production (Islam et al. 2015). enter the environment by anthropogenic sources, includ-
Aquatic ecosystems around the world have been affect- ing industrial and domestic effluents, surface water run-
ed by both natural and anthropogenic activities (Jain off, landfill leachate, atmospheric source, and water
2004; Zhang et al. 2009; Rahman et al. 2014; Nazeer transport (Arain et al. 2008).
et al. 2014; Wang et al. 2015). Heavy metals are one of In aquatic systems, heavy metals are present in water
the most common pollutants which have adversely im- bodies as different species, such as dissolved ions or
pacted many aquatic ecosystems (Ali et al. 2013). complexes, suspended solid, and colloid ions. Reliable
Heavy metals can pose high risk to ecosystems due to measurements of metal fractionation are needed when
their persistent, biogeochemical effects, ecological im- the behavior of trace metals in rivers are studied. A
pacts, and bio-accumulative and non-biodegradable na- number of methods are used for the metals speciation
ture (Jain 2004; Wang et al. 2015). in water system, including ion exchange (Chelex-100)
The bioavailability and toxicity of heavy metals are techniques for labile Amberlite XAD resins and anion
affected by water chemistry. Concentration of metal macroporous resin AG MP-1 for organic. Different
ions are strongly governed by biological processes, methods showed variation in the metal fractionation
redox potential, ionic strength, pH, activities of organic using the various techniques. In the present study,
and inorganic chelators, and scavenging processes chelex-100 and AG MP-1 technique, developed by
(Arain et al. 2008; Yang et al. 2012). The behavior Jiann and Presley (2002), which is a more common
of heavy metals in aquatic environment depends large- method for metal fractionation in water system was
ly on their physico-chemical forms. Moreover, season- used.
al variation may also affect the exchange process Lake Pontchartrain is the largest Gulf Coast estuary
between sediment and water directly and indirectly in coastal Louisiana, USA and is considered a highly
(Shomar et al. 2005). Metals are redistributed naturally valued water resource. It is located near dense popula-
in the environment by both geologic and biologic tion and industrial areas along the lower Mississippi
cycles. Many metals, especially those present in aquat- River, Amite River, Tickfaw River, Tangipahoa River,
ic environment, are known to accumulate in plant and Tchefuncta River, Lacombe Bayou, Liberty Bayou,
animal tissues to very high levels, posing a potential Blind River, and Industrial Canal. The water in these
risk to the organisms or even higher organisms in the rivers empties into Lake Pontchartrain, except the Mis-
food chain including humans (Abel 1998; Islam et al. sissippi River. The effects of influxes of these river
2007). Evidence of heavy metal toxic effects has been waters have created uncertainties and controversies
reported on fish and consumers of the contaminated about its environmental impact to the estuary
food (Pourang et al. 2005). (DeLaune et al. 2009). The contaminants, including
The most important trace and toxic elements from an heavy metals, in these rivers water pose a potential risk
aquatic pollution perspective are Cd, Co, Cr, Cu, Mn, to the ecosystem in Lake Pontchartrain. But few studies
Ni, Pb, and Zn. Some of these metals (e.g., Co, Cr, Cu, have been reported on the metal source of these rivers or
Ni, and Zn) are also essential trace nutrient for living water bodies in the Lake Pontchartrain Basin.
organisms to carry out their biological processes but are The present study aimed to investigate the concentra-
toxic at high concentration (Nazeer et al. 2014). Others, tion of heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn)
such as Cd and Pb have no known effects on biological and their speciation in the main streams of Pontchartrain
activity. It has been reported that Cd, Cu, Pb, and Zn can Basin. Furthermore, the bioavailability and toxicity of
bio-accumulate in aquatic organism, leading to metal heavy metals were also assessed by different methods.
Environ Monit Assess (2016) 188:628 Page 3 of 14 628

Materials and methods in an insulated cooler containing ice and deliv-


ered to the laboratory the same day and kept at
The research focuses on several water quality 4 °C before processing and analysis. For each
parameters, including temperature, pH, electrical water samples, one bottle was used for heavy
conductivity (EC), dissolved oxygen (DO), turbid- metal partition analysis, another one for dissolved
ity, DOC, major anions, e.g., F−, Cl−, Br−, NO3−, heavy metal, anions, turbidity, and DOC analysis.
and SO42−, and eight trace metals (Cd, Co, Cr,
Cu, Mn, Ni, Pb, Zn) partitioning at eight rivers in Water analysis
the catchment area of Lake Pontchartrain plus the
Mississippi River adjacent to the western portion The river water sample physico-chemical parame-
of the Basin. The data obtained in our studies ters including pH, EC, DO, and temperature were
were compared with the guideline values sug- measured in situ with a hand-held YSI (Model
gested by World Health Organization (WHO 556, YSI Inc. USA) at 10 cm below the water
2011). surface, and the turbidity was analyzed using
Hach Turbidimeter in laboratory. The water sam-
Water sampling and pretreatment ples for DOC and dissolved items measurement
was passed through a 0.45-μm pore size filter
Eight sampling sites were chosen in the Lake membrane. The DOC was determined in labora-
Pontchartrain Basin, Amite River, Tickfaw River, tory using Shimadzu TOC-V vch Total Organic
Tangipahoa River, Tchefuncta River, Lacombe Carbon Analyzer. The dissolved anions were mea-
Bayou, Liberty Bayou, Blind River as well as sured using Dionex ICS 2000 Ion Chromatograph.
Industrial Canal. Also, samples were collected The dissolved heavy metals were analyzed by
from the Mississippi River, which does not dis- ELAN9000 ICP-MS (PERKINELMER SCIEX)
charge into Lake Pontchartrain, except during after HNO3 acidification.
major flood event in which flood water is
diverted into the Lake Pontchartrain through the Heavy metal partitioning analysis
Bonnet Carre Spillway. The nine sampling loca-
tions are shown in Fig. 1. The water samples The labile and organic fractions in dissolved
collected on 10th February and 9th June 2009, phase were determined based on a partitioning
which represent the spring and the summer procedure using resin column (Jiann and Presley
months, respectively. The water samples were 2002), as shown in Fig. 2. Aliquots of 2.0 g of
collected and stored in two 1000 mL polypropyl- Chelex-100 (analytical grade, 100–200 mesh, so-
ene bottles. Water samples collected were stored dium form) and 1.0 g of AG MP-1 (analytical

Fig. 1 The sampling sites distribution in the associated rivers of Lake Pontchartrain
628 Page 4 of 14 Environ Monit Assess (2016) 188:628

Packing Chelex-100 and AG MP-1 columns with dilute HNO3


The bed volumes of the columns were 4.0 mL (ID
7 mm, length 10 cm) for Chelex-100, varying through-
Washing the two columns with NH4OH, transform the Chelex-100 and
out the sample passing process, and 1.56 mL (ID 7 mm,
AG MP-1 Resin to NH4+ and OH- forms respectivly.
length 4 cm) for AG MP1 (1.0-g packing amounts),
giving contact times of 10–20 s at flow rates of 2–
Washing the resin columns with DI water and connecting the two
3 mL min−1. The species separated by the described
columns in series with Chelex-100 on top, AG MP-1 beneath it.
ion exchange method are operationally defined as labile
(Chelex-100), organic (AG MP-1), and inert (with re-
Using peristaltic pump to drive the water sample go through the
spect to Chelex-100 and AG MP1 resins). The eluent
connected columns. The flow rate were controlled at 2~3ml/min.
was quantified for volume and analyzed using ICP-MS
After all the sample passed through the column set, the columns were or ICP-AES.
disconnected and washed with DI water.

Analytical quality control


Washing the columns with NH4Ac, removing the major
ions(Na+,Ca2+,Mg2+,K+) from the target elements. The ELAN9000 ICP-MS was used to detect the water
heavy metal concentration, and its detection limit for
Washing the columns with DI water again.
Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn were 0.02, 0.001,
0.05, 0.005, 0.002, 0.004, 0.004, and 0.02 μg L−1, re-
The trace metals adsorbed on the Resin columns were eluted by dilute
spectively. The heavy metal concentration in river water
HNO3. Counting the volume of the eluent and then analyzing the
ranged within the instrumental detection limits. The
solution with ICP-MS or ICP-AES.
anion detection limits of Dionex ICS 2000 Ion Chro-
matograph for F−, Cl−, Br−, NO3−, and SO42− were 3,
Fig. 2 The process flow diagram of trace metal partition 10, 3, 10, and 10 μg L−1, respectively. All reagents for
treatment of samples during heavy metal analysis were
grade, 100–200 mesh, chloride form), both weighed suprapure or ultrapure grade, supplied by Sigma-
out directly from original packing, were separately Aldrich (USA). All solutions were prepared using
slurry packed into Poly-Prep columns (Bio-Rad) in Milli-Q deionized water. For quality control, analytical
2 N HNO3. Resins were converted to NH4+ and OH− blanks and certified reference (Lab Quality Control
forms, respectively, by washing each column with Standard, QC-2 and QC-4) with known concentrations
10 mL of 1 M NH4OH solution. After being washed (5 and 10 ppb for every element) were prepared and
with distilled water, the two columns were connect- analyzed using the same procedures and reagents. The
ed with the Chelex-100 column on top. Each sample QC-2/QC-4 was run at an interval of 15 samples, and if
was then connected to a column placed through a the relative differences of any element were more than
50-cm section of silicon tube, with the sample bottle 20 %, the process should be stopped and cross checked.
being set 30 cm higher than the top of the column The results of our determination were acceptable.
set, flow was initiated by gravity, and flow rates
were controlled at 2–3 mL min−1 by two-way stop-
cocks. After each sample passed through the column Results and discussions
set, the columns were disconnected and washed with
distilled water (2 × 5 mL). Major ions (Na, Ca, Mg, Physico-chemical properties of water
K) were separated from target elements by washing
the columns with 5 × 4 mL of 1 M ammonium The physico-chemical characteristics of water samples
acetate at pH 5.5. After washing again with distilled collected from the different water bodies are summa-
water (2 × 5 mL), trace metals were eluted by 7 mL rized in Tables 1 and 2.
of 2 N HNO 3 . This procedure resulted in pre- The data showed that the pH during spring is com-
concentration factors of up to 150 with a 1000-mL paratively higher than the summer in water samples
sample and has the advantage of one-step pre-con- collected from the different rivers. The pH was slightly
centration yielding two fractions of trace metals, in a acidic (6.37–7.03) and alkaline (7.20–8.07) during sum-
medium free from matrix interference. mer and spring, respectively. The water pH within the
Environ Monit Assess (2016) 188:628 Page 5 of 14 628

Table 1 Physico-chemical characteristics of river water

River name pH EC (μS cm−1) Temperature (°C) DO (mg L−1) Turbidity (NTU) DOC (mg L−1)

Spring Summer Spring Summer Spring Summer Spring Summer Spring Summer Spring Summer

Mississippi River 7.71 6.44 266.8 359.9 5.80 26.4 15.5 5.29 46.3 24.23 18.3 14.8
Amite River 7.69 6.68 136.3 166.9 14.8 27.7 7.77 5.80 14.3 7.71 16.3 8.27
Tickfaw River 7.78 6.67 88.60 112.5 15.9 26.0 8.14 6.30 16.7 17.2 13.8 6.21
Tangipahoa River 7.20 6.76 45.30 55.80 16.80 27.6 7.92 9.53 7.30 11.4 5.02 6.82
Tchefuncta River 7.42 7.03 2961 1976 15.6 28.6 8.26 6.77 6.24 4.32 12.2 16.7
Lacombe Bayou 7.45 6.79 4660 3941 17.8 30.0 8.41 8.24 4.42 3.72 16.7 24.8
Liberty Bayou 8.07 6.76 6590 6590 17.3 30.1 10.3 5.32 8.55 6.69 23.5 16.2
Blind River 7.99 6.37 503.0 1254 16.2 28.1 4.47 2.64 11.5 20.3 41.0 30.7
Industrial Canal 7.78 6.53 10,170 10,110 14.7 28.2 8.09 6.66 3.78 3.57 15.4 11.7
−1
Public supply 6.5–8.5 1.3 (mS cm ) NS >4
Recreation 6.5–8.5 4
Aquatic life 6.5–9.0 8–28 5.5
Irrigation 6.5–8.5 3000 >4
WHO (2011) 7.0–8.5 750 (μS cm−1) 6

NS no health-based guideline values recommended

safe limit (6.5–8.5) is acceptable for outdoor bathing pH affects biochemical processes and is an important
and considered safe for the skin and organs like eyes, indicator of environmental quality and pollution level in
nose, and ears (Sharma et al. 2014). Similar trend in pH water system (Singh et al. 2005; Kannel et al. 2007;
was reported by Islam et al. (2015). Precipitation of Nazeer et al. 2014). The acidic nature of river water
dissolved of Cd and other cations could be a possible would have no detrimental effects on the water quality
reason for the higher pH in the spring (Jain 2004). The and to organisms, which emphasizes the need to pay

Table 2 The concentration of anions in river water of Lake Pontchartrain Basin (mg L−1)

River name F− Cl− Br− NO3− SO42−

Spring Summer Spring Summer Spring Summer Spring Summer Spring Summer

Mississippi river 0.1112 0.0054 34.66 19.03 1.252 0.2937 8.614 5.660 40.09 29.52
Amite River 0.0532 0.0995 37.50 35.68 0.4045 0.4702 1.111 0.1844 5.740 4.481
Tickfaw River 0.0629 ND 11.31 20.80 0.4482 0.3753 0.7023 2.466 6.680 6.649
Tangipahoa River 0.0454 0.0750 5.567 14.04 0.4348 0.3250 1.243 1.977 1.833 1.466
Tchefuncta River 0.2135 0.3270 1517 495.4 5.081 3.740 2.916 2.810 134.8 65.83
Lacombe Bayou 0.1456 0.3790 2261 954.0 7.081 6.419 0.2366 3.245 198.4 134.7
Liberty Bayou 0.2059 0.3510 2397 1542 8.977 8.891 0.0990 2.617 257.3 233.0
Blind River 0.1969 ND 170.7 301.9 1.385 4.057 1.005 2.822 9.711 17.91
Industrial Canal 0.2678 ND 4139 2961 13.98 25.66 2.560 8.891 547.1 419.1
Public supply (mg L−1) 5 10 400
Recreation (mg L−1) 400
Aquatic life (mg L−1) 120 2.93
Irrigation (mg L−1) 100–250 10 960
WHO (mg L−1) 1.5 200 0.01 11 250

ND not detectable, NA not available


628 Page 6 of 14 Environ Monit Assess (2016) 188:628

attention to river water in spring (Wang et al. 2015). The possible reason of high turbidity in these rivers, which
alkaline pH in Liberty Bayou may possibly be attributed lead to high turbidity from water disturbance. The
to the disposal and delocalization of industrial wastes, highest turbidity (46.3 NTU) and DO (15.5 mg L−1)
domestic waste water contamination, presence of chem- reported in Mississippi River is likely due to the carriage
ical detergent, release of bicarbonate, carbonate ions, of the suspended sediment load of the drainage basin
and limestone bed rocks (Mona and Shuchi 2012; (Alonso et al. 2004). The measured DOC was generally
Vieira et al. 2013; Sharma et al. 2014). Overall, the pH higher during spring than summer in most rivers. Higher
in all the rivers during both seasons is within the pre- temperature in summer favors the microbial degradation
scribed standards. The EC was higher during summer. of organic matter and decrease DOC in the water. The
Higher EC level during summer indicate higher salinity samples collected from Tangipahoa River, Tchefuncta
in the rivers. High salinity can also be attributed to high River, and Lacombe Bayou showed higher DOC during
evaporation in summer, which accelerates the accumu- summer than in spring. A possible reason may be the
lation of salts in water (Jiang et al. 2015). The EC of disposal of sewage and industrial wastes in these rivers
Tchefuncta River, Lacombe Bayou, Liberty Bayou, (Jain 2004).
Blind River, and Industrial Canal is higher than the
standard of WHO limits (750 μS cm−1), reflecting pos- Anions concentration in river water
sible higher pollution level, and/or salt water intrusion
from the lower basin and its unsuitability for drinking The anions concentration in the water samples collected
purposes (WHO 2011; Mona and Shuchi 2012; Sharma from the Lake Pontchartrain Basin is presented in Ta-
et al. 2014). The high EC could also be due to higher ble 2. The anion contents were higher in case of F−, Cl−,
concentration of prevalence of ions like Cl− shown in and NO3−, in the summer, whereas Br− and SO42− were
Table 2. River water temperature was higher during greater in the spring. The F− level was below the WHO
summer than the spring months. The longer photoperiod standards (1.5 mg L−1) in all the rivers for both seasons,
in summer increases the temperature of the river water. showed no likely adverse effects to aquatic life and the
As a result, the rising temperature not only affects the environment (WHO 2011). The Cl− content was greater
solubility of the ions in water bodies but also increased than health-based guideline value (5 mg L−1) and fresh
EC by evaporation of river water. The temperature was water aquatic life, irrigation, and WHO standards (100–
within the limit (8–28 °C), which favors aquatic life 250 mg L−1) in the Tchefuncta River, Lacombe Bayou,
during both seasons. The DO during spring sampling Liberty Bayou, Blind River, and Industrial Canal. This
was higher than summer months, except for the demonstrates the potential high risk of Cl− ion and salt
Tangipahoa River. It is believed that the higher temper- introduction into these rivers, which led to higher EC
ature in summer contributes to the reduction of DO in values as shown in Table 1. Higher Cl− ion concentra-
the water. DO and temperature are inversely correlated tion is attributed to discharge from domestic sewage
for all sampling sites. DO concentration was lower (Sharma et al. 2014).
during summer and higher in spring months. The deple- The NO3− concentration was lower than the WHO
tion of oxygen could influence biological activities and permissible level (10 mg L−1) for drinking in all the
reduces oxygen solubility supported by the warmer rivers during both seasons. Meanwhile, the concentra-
temperature. Moreover, when water temperature in- tion of NO3− was higher than the permissible limit for
creases, DO holding capacity of water can decrease aquatic life (2.93 mg L −1 ) in Mississippi River,
due to rapid saturation (Hou et al. 2013). The observed Lacombe Bayou, and Industrial Canal during spring
low DO (<5 mg L−1) values, especially in Blind River and summer, respectively. The SO42− concentration
during summer and spring showed the poor water qual- was lower than international standard limit in all the
ity and unsuitability for drinking (Sharma et al. 2014). rivers, except Liberty Bayou and Industrial Canal. The
Our results are in consensus with the work of Kong and SO42− concentration was higher in these two rivers than
Ye (2014), who also reported a positive correlation the WHO standards (250 mg L−1) during both seasons.
between elevated temperature and decreased DO. Anthropogenic activities like fertilizer use, domestic
The water turbidity reported in this study was gener- sewage, atmospheric sources, and salt water intrusion
ally higher during spring than the summer. Fresh water could be responsible for the higher concentration
introduction from major rainfall events might be a (Sharma et al. 2014). A possible reason for the
Environ Monit Assess (2016) 188:628 Page 7 of 14 628

fluctuation is that anions can be sensitive to temperature Pontchartrain. But the highest Cd content (0.35 μg L−1)
changes. It is obvious from Tables 1 and 2 that EC, F−, was measured in the Tchefuncta River. This could be
Cl−, and NO3− was higher in the summer. As compared due to the lower flow rate of water leading to the
with the spring, anthropogenic activities might also be a precipitation of the metals (Islam et al. 2014).
possible source of anions in river water (Alonso et al. The Co concentration was higher in all the rivers
2004). Klavins et al. (2000) reported seasonal changes during summer as compared with the spring except for
in water chemistry and the heavy metal fraction profile. the Tickfaw River, Tangipahoa River, and Tchefuncta
Our research findings showed the anion concentration River. The lowest and highest Co content (0.2,
decreased in the order of Cl− > SO4− > NO3− > Br− > F−. 0.85 μg L−1) during spring was reported in Tangipahoa
These findings are supported by work of Sharma et al. and Blind River, respectively. While, in the summer
(2014) on the Ganges River. Our findings are also in sampling, the lowest and highest Co content (0.15 and
consensus with the reported global mean anion concen- 1.25 μg L−1) were measured in the Tangipahoa and
trations (Jiang et al. 2015). Major ion sources are mainly Blind River, respectively. These findings show that
derived from atmospheric deposition, chemical Tangipahoa and Tchefuncta River are less polluted with
weathering of rocks, evaporation-crystallization pro- Co, as compared with the other rivers in the study area.
cess, and anthropogenic input in rivers. Runoff from Based on our findings, the concentration of Cr was
the agricultural fields, domestic sewage, and salt water higher in spring than in summer, except for the
intrusion from the lower basin of coastal system could Tchefuncta River. The Cr concentration during spring
contribute to the increased level of these ions (Sharma fluctuated between 6.15 and 7.3 μg L−1in the Tickfaw
et al. 2014; Jiang et al. 2015; Zhang et al. 2016). River and Industrial Canal, respectively. In contrast,
only a minor decrease was measured in all the other
Temporal variation in concentration of dissolved heavy rivers during summer. The concentration of Cr was
metals in river water higher in the Tchefuncta River during summer. The Cr
concentration during spring and summer was higher
The seasonal variation in the concentration of dissolved than the reported WHO standard level (5 μg L−1) for
heavy metals in water samples collected from nine drinking water and lower than TRV (11 μg L−1) (WHO
different rivers in Lake Pontchartrain Basin is presented 2011; USEPA 1999). These finding suggest that water
in Table 3. Frequent use of polluted river water increases of the streams associated with Lake Pontchartrain are
the risk to human health. WHO has reported about 80 % not suitable for drinking purpose. Similar results were
of human diseases, caused by drinking contaminated reported for the Korotoa River by Islam et al. (2015).
water (Sharma et al. 2014). All heavy metals (Cd, Co, The discharge of untreated sewage, poultry, and indus-
Cr, Cu, Mn, Ni, Pb) except Zn showed higher concen- trial wastes could be a possible reason for the higher
tration during the spring than summer sampling. The concentration of Cr in the rivers (Facetti et al. 1998;
concentrations of heavy metals were compared with the Kansal et al. 2013).
international protocols, including toxicity reference val- Cu concentration was generally higher during
ue (TRV) (USEPA 1999), WHO (2011), USEPA Drink- spring than the summer in all rivers except for the
ing Water (2006), USEPA Aquatic Life Protection Wa- Tangipahoa and Tichfaw rivers. The maximum con-
ter Quality Standards (Nazeer et al. 2014). centration (4.05 and 4.0 μg L−1) during spring was
The Cd concentration was higher in spring than the measured in the Tichfaw and Tangipahoa rivers, re-
summer in all the rivers except the Tchefuncta River and spectively. The Cu concentration was generally the
Blind River. The same Cd level (0.2 μg L−1) during same during spring and summer in the Tangipahoa
spring was measured in the Mississippi River, Amite River. In summer, the concentration fluctuated
River, Liberty Bayou, and Industrial Canal. The lowest between 2.15 and 4.2 μg L −1 in the Amite and
Cd content (0.1 μg L−1) was measured at the remaining Tangipahoa rivers. The concentration of Cu was lower
stations. In summer, 0.1 μg L−1 Cd was measured in than the reported WHO and TRV levels (2000,
most of the rivers. The Cd concentration was lower in all 9000 μg L−1, respectively). These findings suggest
rivers than the standard values of TRV (2000 μg L−1) low pollution risk from Cu in the catchment area asso-
and WHO (3 μg L−1), indicating low Cd pollution in the ciated with the Lake Pontchartrain Basin. The high Cu
catchment area, leading to low enrichment of Cd in Lake content might be due to domestic sewage and runoff
628
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Table 3 The concentration of dissolved heavy metals in river water in spring and summer (μg L−1)

Sample name Cd Co Cr Cu Mn Ni Pb Zn

Spring Summer Spring Summer Spring Summer Spring Summer Spring Summer Spring Summer Spring Summer Spring Summer

Mississippi River 0.21 0.20 0.30 0.75 6.60 6.10 2.75 2.40 1.40 25.0 1.30 2.45 6.85 5.2 34.4 252
Amite River 0.20 0.05 0.45 0.80 6.50 5.75 3.10 2.15 84.8 35.0 2.60 1.9 3.8 4.45 65.0 108
Tickfaw River 0.10 0.05 0.75 0.55 6.15 6.10 4.05 3.50 131 107 1.70 1.7 5.5 2.55 145 101
Tangipahoa River 0.15 0.15 0.20 0.15 6.8 6.45 4.00 4.20 80.3 54.0 2.50 2.75 5.6 5.3 78.4 228
Tchefuncta River 0.10 0.35 0.40 0.25 6.65 7.05 2.50 2.90 42.2 11.0 3.00 2.85 6.55 5.7 40.5 117
Lacombe Bayou 0.15 0.10 0.25 0.70 7.15 6.40 3.65 3.10 28.4 31.0 2.50 2.3 5.35 4.2 31.8 120
Liberty Bayou 0.20 0.10 0.45 0.50 7.30 6.85 2.95 2.45 22.5 23.0 2.70 2.05 8.15 6.05 31.2 70.0
Blind River 0.05 0.15 0.85 1.25 6.95 6.15 3.70 3.45 285 401 2.00 3.05 6.6 3.55 33.1 528
Industrial Canal 0.20 0.10 0.40 0.75 7.30 6.55 3.20 3.20 2.60 12.0 2.10 2.15 8.45 7.4 24.7 338
TRV (mg L−1) 2 (2000) NA 11 (11,000) 9 (9000) NA 52 (52,000) 3 (3000) NA
Public supply (mg L−1) 0.05 (50) NA 0.05 (50) 1.5 (1500) NA 0.1 (100) 0.05 (50) 5 (5000)
Recreation (mg L−1) 0.01 (10) NA 0.05 (50) 1.5 (1500) NA NA 0.01 (10) 15 (15,000)
Aquatic (mg L−1) 0.001 (1) NA 0.05 (50) 0.007 (7) 0.1 (100) 0.005 (5) 0.01 (10) 0.086 (86)
Irrigation (mg L−1) 0.010 (10) NA 0.01 (10) 0.2 (200) 0.2 (200) 0.2 (200) 0.1 (100) 2 (2000)
USEPA Drinking (mg L−1) 0.005 (5) NA 0.1 (100) 1.3 (1300) NA 0.1 (100) 0.015 (15) 2 (2000)
USEPA Aquatic life protection 0.001 (1) NA 0.16 (160) 0.004 (4) 0.050 (50) 0.145 (145) 0.014 (14) 0.050 (50)
(mg L−1)
WHO (2011) (mg L−1) 0.300 (3) 0.4 (400) 0.050 (50) 2 (2000) 0.1 (100) 0.070 (70) 0.010 (10) 0.5 (500)

Values in parenthesis show the standard values in micrograms per liter. WHO (2011) drinking water standards
TRV toxicity reference value for fresh water proposed by USEPA (1999), NA not available
Environ Monit Assess (2016) 188:628
Environ Monit Assess (2016) 188:628 Page 9 of 14 628

from farmed lands (Byrne and DeLeon 1987; Flocks concentration of Zn was higher than CCME limit
et al. 2009; Islam et al. 2014). (50 μg L−1) during summer in all the rivers (CCME
Measured Mn content was higher during summer 2007). This might be due to the high solubility of Zn at
than spring in most cases. Mn and Co followed the same higher temperatures. Similar trend in the concentration
trends in Lacombe Bayou, Liberty Bayou, Blind River, of Zn was reported by Harguinteguy et al. (2014).
and Industrial Canal. The lowest and highest Mn content Overall, our findings reflect that the concentration of
(11, 401 μg L−1) was reported in Tchefuncta River and dissolved metals in the different rivers was higher dur-
Blind River, respectively, during the summer. In spring, ing spring than summer due to the lower water flow in
the lowest and highest Mn content (1.4, 131 μg L−1) was winter, which could help to accumulate/precipitate the
measured in the Mississippi and Tichfaw rivers, respec- heavy metals at high levels (Islam et al. 2014). The
tively. The low temperature (5.8 °C) might be the reason lower levels of trace metals (Cd, Co, Cu, and Ni) during
for low solubility of Mn in Mississippi in the spring. The summer might be due to the dilution effect of additional
Mn concentration was higher than the standard values of rain water in river (Mohiuddin et al. 2012; Islam et al.
WHO and USEPA Aquatic life protection standards 2015). Differences in the concentration of the heavy
(50–100 μg L−1) in the Amite River, Tickfaw River, metals during different seasons have also been reported
Tangipahoa River, and Blind River (WHO 2011; Nazeer by Vega and Weng (2013).
et al. 2014). These findings show the unsuitability of the
water for drinking purpose as well as posing as a poten- Trace metal partitioning in river water
tial high risk to aquatic life in these rivers. Anthropo-
genic activities might be potential sources of Mn in the The trace metals can be categorized into three categories
Lake Pontchartrain Basin (Herndon and Brantley 2011). namely, labile, organic, and inert forms. The speciation
Ni concentration was higher during spring than sum- pattern of trace metals (Cd, Co, Cr, Cu, Mn, Ni, Pb, Zn)
mer in all the rivers. The Ni concentration during spring in the water samples of different rivers in Lake
ranged from 1.3 to 3.0 μg L−1 in the Mississippi and Pontchartrain Basin is given in Fig. 3.
Tchefuncta rivers, respectively. In summer, the Ni level The variation in the forms of Cd can be observed in
was greater in Blind River than the highest concentra- both seasons. The organic form of Cd has increased in
tion (3.0 μg L−1) during spring and remained constant in the Amite River, while the labile and organic forms
Tickfaw River during both seasons. The Ni level was far decrease at Tchefuncta River in summer. The highest
less than the reported TRV and WHO standards for labile form was observed in spring in the Amite River,
drinking water (70 and 52,000 μg L−1, respectively), which decreased in summer. On average, the inert form
representing a low risk for Ni pollution in Lake (57.59 and 55.29 %) was in greater proportion followed
Pontchartrain Basin (USEPA 1999; WHO 2011). by labile (33.11, 35.60 %) during both summer and
Pb levels were higher during spring than summer, spring. The organic form was the lowest fraction (9.22,
excluding the Amite River. Meanwhile, Pb content in 9.10 %) in both seasons. The organic speciation was
Industrial Canal was higher (8.45 and 7.4 μg L−1) than assumed to be affected by pH and temperature in the
all other rivers for both seasons. The highest and lowest Amite River and Tchefuncta River. In fresh water sys-
Pb concentration (8.45, 3.8 μg L−1) was measured in tem, the organic is the greater fraction, which is bio-
Industrial Canal and Amite River during spring, respec- available (Perdue 1997).
tively. The concentration of Pb in both seasons was The Co content is dominated by the inert form
lower than TRV (USEPA 1999) and WHO (2011) stan- (94.92, 96.1 %) followed by organic (3.10, 1.85 %) in
dards (10, 3000 μg L−1, respectively) for drinking water, summer and spring. A slight increase was measured in
showing low Pb risk from water pollution. the organic fraction of Co at Tangipahoa River and
Only Zn level was higher during summer than spring. Tchefuncta River in summer. Labile was the lowest
This finding is obviously against the trends followed by fraction in the water (1.973, 2.049). The variation in
all other metals in the present study. The highest and organic fraction is associated with pH of river water. Our
lowest (528, 70.0 μg L−1) Zn was observed in Blind findings as confirmed by Jiann and Presley (2002), who
River and Liberty Bayou, respectively. Only Blind Riv- also reported 95 % inert fraction in Texas River system.
er had a higher concentration than the WHO standard The Cr concentration was dominated by inert fraction
limit (500 μg L−1) during summer. In general, the (97.01, 96.83 %), while the organic and labile fraction
628 Page 10 of 14 Environ Monit Assess (2016) 188:628

120

River water Cd partition in Summer (%)


120

River water Cd partition in Spring (%)


Inert form Organic form Labile form
Inert form Organic form Labile form
100 100

80 80

60 60

40 40

20 20

0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Rivers Rivers

120 120

River water Co partition in Summer (%)


River water Co partition in Spring (%)

Inert form Organic form Labile form Inert form Organic form Labile form
100 100

80 80

60 60

40 40

20 20

0 0
1 23 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Rivers Rivers

120 120
River water Cr partition in Summer (%)
River water Cr partition in Spring (%)

Inert form Organic form Labile form Inert form Organic form Labile form
100 100

80 80

60 60

40 40

20 20

0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Rivers Rivers

120 120
River water Cu partition in Spring (%)

River water Cu partition in Summer (%)

Inert form Organic form Labile form Inert form Organic form Labile form
100 100

80 80

60 60

40 40

20 20

0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Rivers Rivers

Fig. 3 The concentration of trace element partition of river water in spring and in summer
Environ Monit Assess (2016) 188:628 Page 11 of 14 628

River water Mn partition in Summer (%)


120 120

River water Mn partition in Spring (%)


Inert form Organic form Labile form Inert form Organic form Labile form
100 100

80 80

60 60

40 40

20 20

0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Rivers Rivers

120 120

River water Ni partition in Summer (%)


River water Ni partition in Spring (%)

Inert form Organic form Labile form Inert form Organic form Labile form
100 100

80 80

60 60

40 40

20 20

0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Rivers Rivers

120
River water Pb partition in Summer (%)

120
River water Pb partition in Spring (%)

Inert form Organic form Labile form Inert form Organic form Labile form
100 100

80 80

60 60

40 40

20 20

0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Rivers Rivers

120 120
River water Zn partition in Summer (%)
River water Zn partition in Spring (%)

Inert form Organic form Labile form Inert form Organic form Labile form
100 100

80 80

60 60

40 40

20 20

0 0
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Rivers Rivers
Fig. 3 (continued)
628 Page 12 of 14 Environ Monit Assess (2016) 188:628

remained nearly the same during summer and spring. Co concentrations might be attributed to human activities,
and Cr followed the same trend during summer and leading to increase potential toxicity in these rivers.
spring. The EDTA or organic ligands (humic materials) The Zn fraction showed major differences as com-
have strong affinity for trace metal ion attachment, pared with the other metals. The labile and inert fraction
which may elevate the inert fraction (Jiann and Presley was higher (52.85, 17.01, and 45.92, 82.71 %) during
2002). spring and summer, respectively. The organic fraction
The Cu fractions fluctuated in both the summer and was nearly negligible in all the rivers in summer. Fig-
spring samples. From Fig. 3, it is obvious that the labile ure 3 shows potential greater risk from Zn pollution in
form of Cu was greater in the summer than spring in the spring than in summer. The higher proportion of dis-
Mississippi River, Tchefuncta River, Lacombe Bayou, solved Zn in summer in rivers seems to be the accumu-
Liberty Bayou, and Blind River. Similarly, the organic lation of inert form, likely influenced by human activi-
fraction was greater during summer as compared with ties. Similar findings were reported in the Texas river
spring season in these rivers. But, on average, the inert system by Jiann and Presley (2002).
fraction (46.75, 68.39 %) was dominant over labile The trace metals fraction shows a decreasing order of
(33.28, 18.13 %) and organic (20, 13.48 %) in spring inert > labile > organic. Overall, the inert fraction con-
than in summer. Inert fraction of Cu could be influenced tributes more than the other fractions, being detrital and
by anthropogenic activities in the upstream of the water can be assumed to be added by natural sources. Labile
bodies. As shown in Table 1, spring had higher DOC metal fraction is potentially the most toxic and of greater
levels than in summer, which favors the formation of concern in natural water system. The organic fraction is
strong complexes of Cu with natural organic matter affected by the redox potential and pH of the river water
(Jiann and Presley 2002; Nazeer et al. 2014). which leads to the release of labile fraction and pose a
The Mn concentration was mostly dominated by inert potential risk to aquatic life (Jain 2004).
fraction (87.14, 84.29 %) in both seasons, with surpris-
ingly high organic content during spring at in the Mis-
sissippi river. The highest organic and labile content was Conclusion
measured in the Mississippi River and Blind River
during spring and summer, respectively. The labile frac- Our research shows the seasonal variations in the
tion remained almost the same in most of the river physico-chemical properties, anions, and the heavy met-
waters, except for Blind River in the summer. The lower al (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn) concentration in
organic content of Mn might be the reason that natural water samples collected from different rivers. Among
organic fraction is <10 % (Jiann and Presley 2002). physico-chemical properties, pH, DO, and turbidity
The inert and labile fraction (47.51, 43.60 %) of Ni were higher during spring, while, EC, temperature, and
was greater than the organic form (8.87 %) in spring, DOC were higher during summer. The anion data re-
while the labile fraction (57.66 %) was greater during vealed that the concentration of F−, Cl−, and NO3− was
summer over the inert and organic form (31.62, higher during summer and Br− and SO4− was reported
10.76 %). On average, the organic form was greater higher during spring. Our research findings showed
during summer as compared during spring. The higher anion concentration were in the order of
labile fraction of Ni, which is vulnerable to small chang- Cl− > SO4 −> NO3− > Br− > F−, which are in consensus
es in environmental conditions, during both seasons with the global mean anion concentration. Runoff from
show the influence of anthropogenic activities and its the agricultural field, domestic sewage, and salt water
potential higher toxicity to the Lake Pontchartrain Basin intrusion from the lower basin might contribute to high
(Florence 1986, 1992; Islam et al. 2015). level of anions.
The Pb fraction was mainly dominated by inert form All the dissolved heavy metals except Zn were higher
in both seasons. The organic fraction was the same in during spring. No potential Cd risk was reported for
both seasons, while, the labile fraction increased from both seasons. During summer, Amite River, Mississippi
6.75 to 19.95 % between spring and summer. The River, Industrial Canal, and Lacombe Bayou showed
highest Pb level was measured at Lacombe Bayou dur- higher Co level. The Cr and Mn levels were higher than
ing summer. On average, the labile Pb fraction increased the WHO standards, while no Cu pollution risk was
in all the rivers during summer. The increase in labile reported. Mn and Co followed the same trend in
Environ Monit Assess (2016) 188:628 Page 13 of 14 628

Lacombe Bayou, Liberty Bayou, Blind River, and In- sediment properties. Aquatic Ecosystem Health and
Management, 12, 456–460.
dustrial Canal. Potentially low Ni risk was likely in river
Dhanakumar, S., Solaraj, G., & Mohanraj, R. (2015). Heavy metal
water during both seasons. Liberty Bayou and Industrial partitioning in sediments and bioaccumulation in commercial
Canal are on the verge of reaching potential Pb pollution fish species of three major reservoirs of river Cauvery delta
levels in the studied rivers. Zn content was higher in region, India. Ecotoxicology and Environmental Safety, 113,
summer in all the rivers than the USEPA aquatic life 145–151.
Facetti, J., Dekov, V. M., & Van Grieken, R. (1998). Heavy metals
standards. Cd, Co, Cu, and Ni showed no pollution risk, in sediments from the Paraguay River: a preliminary study.
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Pontchartrain, Louisiana. Journal of Coastal Research., 54,
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Acknowledgments The project was conducted at School of metal accumulation in leaves of aquatic plant Stuckenia
Plant, Environmental and Soil Sciences, Louisiana State Univer- filiformis and its relationship with sediment and water in the
sity AgCenter. This work was partly supported by a grant through Suquía River (Argentina). Microchemical Journal, 114, 111–
the Lake Pontchartrain Basin Foundation (no. 06-07NOAA-06- 118.
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