2.0  Physical, Chemical, and Biological Characteristics of the
Lower Cape Fear River Estuary

Matthew R. McIver and Michael A. Mallin

 

2.1  Introduction
    This section of the report includes a discussion of the physical, chemical, and biological water quality parameters, concentrating on the 1999-2000 Lower Cape Fear River Program monitoring period. These parameters are interdependent and define the overall condition of the river. Physical parameters measured during this study included water temperature, dissolved oxygen, turbidity, salinity, conductivity, and pH. The chemical makeup of the Cape Fear River was investigated by measuring the magnitude and composition of nitrogen and phosphorus in the water, as well as concentrations of EPA priority pollutant metals. Three biological parameters, fecal coliform bacteria, chlorophyll a and biochemical oxygen demand, were examined to assess the effects of point and non-point source loading of nutrients, organic materials, and other pollutants on water quality.

 

2.2  Materials and Methods
    All samples and field parameters collected for the estuarine stations of the Cape Fear River (i.e. NAV down through M18) were gathered on an outgoing tide. This was done so that the data better represented the river water flowing downstream through the system rather than the tidal influx of coastal ocean water. Sample collection and analyses were conducted according to procedures in the Lower Cape Fear River Program QA/QC Manual.

Physical Parameters

Water Temperature, pH, Dissolved Oxygen, Turbidity, Salinity, and Conductivity

   Field parameters were measured at each site using a YSI 6920 Multiparameter Water Quality Probe (sonde) and displayed on a YSI 610D datalogger. Individual probes within the instrument measured water temperature, pH, dissolved oxygen, turbidity, salinity, and conductivity. At each channel station, physical parameters were measured at the surface, mid-depth, and bottom, or until the cable connecting the datalogger with the sonde had been fully extended. Stream stations were sampled at 0.25 m from surface. High flow occasionally prohibited the probe from reaching the bottom. The instrument was calibrated prior to and after each sampling trip to ensure accurate measurements.

Chemical Parameters

Nutrients
   All nutrient analyses were performed at the Center for Marine Science Research (CMSR, now Center for Marine Science, CMS) for samples collected prior to January 1996. A local state-certified analytical laboratory was contracted to conduct all subsequent analyses (February 1996 through May 2000), except for the orthophosphate procedure which is performed at CMS. The contract laboratory also analyzes for suspended solids, fecal coliform bacteria, and EPA Priority Pollutant Metals according to State-accepted procedures. The following methods detail the techniques used by CMS personnel only.
    Water samples were collected ca. 0.2 m below the surface in triplicate in amber 125 mL Nalgene plastic bottles. After collection, the samples were immediately placed on ice. In the laboratory, 50 mL of each triplicate was filtered through a separate 1.0 micron pre-combusted glass fiber filter, which were frozen and subsequently used for chlorophyll a analysis. The triplicate filtrates were pooled in a common glass flask, mixed thoroughly, and approximately 100 mL was poured into one 125 ml plastic bottle to be used for orthophosphate analyses. Filtered samples were stored in a freezer until time of analysis.

Orthophosphate (PO4-3)
   All orthophosphate analyses were performed in duplicate using an approved EPA (1992) method for the Technicon AutoAnalyzer (Method 365.5). In this technique, the orthophosphate in each sample reacts with ammonium molybdate and antimony potassium tartrate in an acidic medium (sulfuric acid) to form an antimony-phospho-molybdate complex. The complex is then reacted with ascorbic acid and forms a deep blue color. The intensity of the color is measured at a wavelength of 880 nm by a colorimeter and displayed on a chart recorder. Standards and spiked samples were analyzed for quality assurance.

Biological Parameters

Chlorophyll a
   The analytical method used to measure chlorophyll a is described in Welschmeyer (1994) and USEPA (1997). Chlorophyll a concentrations were determined directly from the 1.0 micron glass fiber filters used for filtering samples for orthophosphate analyses. All filters were wrapped individually in aluminum foil, placed in an airtight container with drierite granules, and stored in a freezer. During the analytical process, the glass filters were separately immersed in 10 ml of a 90% acetone solution for 24 hours. The acetone extracts the chlorophyll a from the glass filters into solution. At seven stations an additional grinding step was used during extraction. Each solution was then analyzed for chlorophyll a concentrations using a Turner AU-10 fluorometer. This method uses an optimal combination of excitation and emission bandwidths which reduces the errors inherent in the acidification technique.

Biochemical Oxygen Demand (BOD)
   Five sites were chosen for BOD analysis. One site was located at NC11, upstream of International Paper, and a second site was at AC, about 3 miles downstream of International Paper. A third site was located in Livingston Creek (LVC) near its outflow to the Cape Fear River. Two sites were located in blackwater rivers (NCF117 and B210), and one site (BBT) was situated in an area influenced by both the mainstem Cape Fear River and the Black River (Fig. 1.1). The procedure used for BOD analysis was Method 5210 in Standard Methods (APHA 1995). Samples were analyzed for both 5-day and 20-day BOD. During the analytical period, samples were kept in airtight bottles and placed in an incubator at 20o C. All experiments were initiated within 5 hours of sample collection. Samples were analyzed in duplicate. Dissolved oxygen measurements were made using a YSI Model 57 meter that was air-calibrated. No adjustments were made for pH since all samples exhibited pH values within or very close to the desired 6.5-7.5 range.

 

2.3  Results and Discussion

    This section includes results from monitoring of the physical, biological, and chemical parameters at all stations for the time period June 1999 – May 2000. Discussion of this data focuses mainly on the river channel stations, especially with respect to long term trends. The contributions of the two large blackwater tributaries, the Northeast Cape Fear River and the Black River, are represented by conditions at NCF117 and B210, respectively. Conditions at the stream stations are highly variable and often change rapidly as a result of localized weather phenomena, therefore, definable patterns and trends are not exhibited at these sites. Chronic water quality problems at stream stations are discussed and possible causes are suggested. Hurricanes Dennis and Floyd impacted water quality in the Cape Fear Region on August 29 and September 15, respectively.

Physical Parameters

Water Temperature
   Water temperatures at all stations ranged from 5.3 to 31.9 0C and individual station annual averages ranged from 16.9 to 19.8 0C (Table 2.1). Highest temperatures were found during August 1999 (all station mean = 28.6) and lowest temperatures were occurred during February 2000 (all station mean = 6.6). Stream stations were generally cooler than the river channel stations most likely because of shading and lower nighttime air temperatures affecting temperatures in the shallower waters.

Salinity
   Salinity at the estuarine stations ranged from 0.0 – 35.4 parts per thousand (ppt) and station annual means ranged from 1.3 – 25.3 ppt (Table 2.2). Salinity was lowest during the late summer/fall months, a result of rain from Hurricanes Dennis, Floyd and Irene, and highest during the early/middle summer months. Two stream stations had occasional oligohaline conditions: The Northeast Cape Fear River at NC 403 and Panther Branch both receive salt-water effluent from pickle processing facilities.

Conductivity
   Conductivity ranged from 0.07 to 39.43 mS/cm at the estuarine stations and from 0.02 to 7.66 mS/cm at the other stations (Table 2.3). Temporal patterns for conductivity mimicked those of salinity. Dissolved ionic compounds increase the conductance of surface waters, therefore, conductance decreases with salinity, often reflecting river flow conditions along with rainfall. Conductivity can also indicate point source pollution as contaminates often contain ionic compounds. At several freshwater stations located downstream of point source inputs, conductivities are often higher than expected in non-saline surface waters. BC117 is below a wastewater treatment plant and AC is below a pulp mill discharge.

pH
   pH values ranged from 3.1 to 8.3 and station annual medians ranged from 3.5 to 7.9 (Table 2.4). Median pH expectedly increased from the upper river down into the estuary, where low pH swamp water and high pH seawater mix. No unusually high pH values were recorded at any time. The lowest pH of 3.1 was recorded at the pristine blackwater steam station COL which receives drainage from extensive riparian swamps. Swampwater can have naturally low pH due to high concentrations of organic acids.

Dissolved Oxygen
   Dissolved oxygen problems are a major water quality concern for the Cape Fear River (Mallin et al. 1998a; 1998b; 1999a). Dissolved oxygen (DO) concentrations ranged from 0.2 to 14.2 parts per million (ppm = mg/l) and stations annual means ranged from 4.3 to 9.6 ppm (Table 2.5). Mean annual DO concentrations at the channel stations were slightly higher than the five-year averages and remained above the North Carolina State standard of 5 ppm (Figure 2.1). Dissolved oxygen levels at the channel stations are lowest during summer (Figure 2.2), with the five-year summer average falling below the NC state standard in the upper estuary and the blackwater tributary rivers (Fig. 2.3). Summer levels during 1999 were normal until the arrival of Hurricane Floyd in September (Figure 2.2). Working synergistically to lower oxygen levels are two factors: lower oxygen carrying capacity in warmer water and increased bacterial respiration (or biochemical oxygen demand, BOD) due to higher temperatures. These hypoxic conditions could have negative impacts on the biota in the Cape Fear River (see Chapter 4). The dissolved oxygen sag in the lower river and estuary (Fig. 2.3) begins downstream of the pulp and paper mill and is exacerbated by inputs from the Black River (Fig. 1.1).
    The Northeast Cape Fear and Black Rivers generally have lower dissolved oxygen levels than the mainstem Cape Fear River (Figure 2.4). These rivers are classified as blackwater systems because of their tea colored water. As the water passes through swamps en route to the river channel, tannins from decaying vegetation dissolve in the water, resulting in the observed color. Decaying vegetation on the swamp floor has an elevated biochemical oxygen demand and respiration by the bacteria feeding on this organic matter utilizes oxygen from the water, leading to naturally low dissolved oxygen levels. Runoff from concentrated animal operations (CAOs) may also contribute to chronic low dissolved oxygen levels in these blackwater rivers (Mallin et al. 1998b). In the main river channel, annual mean oxygen levels were highest at the upstream stations NC11 (8.8 ppm) and AC (8.6 ppm) and in the lower estuary at station M23 (7.6 ppm). Lower river and upper estuary stations IC (7.4 ppm), and NAV (7.0 ppm) had the lowest DO levels. Discharge of high BOD waste from a paper/pulp mill just above the AC station, as well as inflow of blackwater from the Northeast Cape Fear and Black Rivers, helps to diminish oxygen in the upper estuary. As the water reaches the lower estuary higher algal productivity, mixing and ocean dilution help alleviate oxygen problems.
    Hurricanes Dennis and Floyd caused DO levels to plummet to anoxic and hypoxic levels in October 1999; all channel stations except NC11 had levels below 5.0 ppm (Table 2.5). The Northeast Cape Fear River suffered extremely low oxygen levels, becoming nearly anoxic at NCF 117, where minor fish kills occurred (see Chapter 7). The low dissolved oxygen levels resulting from Hurricanes Dennis and Floyd were somewhat less severe compared to the levels seen after Hurricane Fran (1996) and Hurricane Bonnie (1998) hit the Cape Fear Region. Recovery of dissolved oxygen to normal levels took about one month (Figure 2.2).
    Several stations were in violation of North Carolina water quality standards based on percent of samples in violation during the year June 1999 – May 2000. Definitions used by the North Carolina Division of Water Quality for use-support consider a water body non-supporting (NS) of its designated use if the water quality standard for a given parameter is in violation > 25% of the time. It is considered partially supporting (PS) if the standard is in violation between 11 and 25% of the time. Stations that can be considered non-supporting for dissolved oxygen (4.0 in blackwater stations and 5.0 in estuarine stations) were NAV, DP, IC, NCF117, ANC, SAR, GS, N403 and SR. Stations considered partially supporting for dissolved oxygen include HB, M61, M54, SPD, BBT, B210, ROC, BCRR, GCO and HAM.

Turbidity
   Turbidity levels ranged from 0 to 167 Nephelometric Units (NTU) and station annual means ranged from 3 to 32 NTU (Table 2.6). Turbidities during this monitoring period were slightly lower than the five-year mean at most channel stations (Figure 2.5). The NC State standard for freshwater of 50 NTU was exceeded on three occasions, at the upstream channel stations. The NC State standard for tidal saltwater of 25 NTU was exceeded on 25 occasions, most often in the upper estuary (Table 2.6). Although rainfall and river flow are positively correlated with turbidity in the Cape Fear River (Mallin et al. 1999a; 1999b), turbidity peaks occur most often in winter and spring (Fig 2.6), the time of lowest rainfall in the Cape Fear Region. It is likely that decreased vegetation and decreased evapotranspiration during the cooler months lead to increased runoff and erosion. The contribution of turbidity by the Northeast and Black Rivers was very low. Typically, blackwater rivers carry a low turbidity load as a result of the settling action that occurs in the extensive riparian swamps bordering these rivers. At NCF117 the annual mean was 4 NTU and at B210 the annual mean was 4 NTU.
    The Cape Fear Region has endured the landfall of five hurricanes since 1996, usually accompanied by high rainfall totals. Hurricanes occurred in July 1996, September 1996, August 1998, August 1999 and September 1999. Only after Hurricane Dennis were high turbidity levels measured (Figure 2.6). Possibly, flooding allowed floodplain sediment settlement, and in some cases dilution from rainfall reduced turbidity loads.
    The high levels of turbidity measured at NC11 (mean=32 NTU, maximum=167 NTU), indicates that a large portion of suspended material is being transported into the Lower Cape Fear River system from upstream areas (Mallin et al. 1999b). Rainfall in the upstream areas of the Cape Fear River has a positive correlation with turbidity in the lower system (Mallin et al. 1999b). Turbidity levels decline downstream before reaching the upper estuary at NAV, where increased turbulence may re-suspend turbidity particles. In the estuary, a turbidity maximum occurs as a result of electrochemical reactions in the water column due to the influence of charged ionic compounds (i.e. salinity). This leads to flocculation of particles (the turbidity maximum) and subsequent downstream settling. In the Lower Cape Fear River system the turbidity maximum occurs somewhere between M54 and M42 during normal flow conditions. Moving oceanward down the estuary, turbidities decline to a low at M18, a result of ocean dilution.
    Note: The LCFRP uses nephelometers designed for field use, which allows us to acquire in situ turbidity from a natural situation. North Carolina Division of Water Quality uses turbidity values from water samples removed from the natural system, put on ice for a number of hours, and analyzed later using laboratory nephelometers. Standard Methods notes that transport of samples and temperature change alters true turbidity readings. Our analysis of samples read using both methods shows that lab turbidity is nearly always substantially lower than field turbidity, although the same process is used (nephelometry). Based on field turbidities, one station, M42, could be rated NS for turbidity, while Stations NAV, HB, BRR, M61, M54, M31, SPD, LRC and BCRR could be rated PS.

Total Suspended Solids
   Total suspended solid (TSS) values ranged from 1 to 191 mg/l, with station annual means from 2 to 22 mg/l (Table 2.7). TSS was highest at the uppermost station NC11 and in the upper estuary at NAV. The lower estuary had generally higher values than the river, most likely a result of increased biological productivity and increased phytoplankton and zooplankton densities. Lowest values were seen in the stream stations and in the blackwater rivers. Highest monthly means for TSS occurred during summer. Both turbidity and TSS peaked after Hurricane Dennis in September. Although total suspended solids (TSS) and turbidity both quantify suspended material in the water column, they do not always agree. High TSS does not mean high turbidity and vice versa. This anomaly may be explained by the fact that fine clay particles are effective at dispersing light and causing high turbidity readings, while not resulting in high TSS. On the other hand, large organic particles may be poor at dispersing light, yet their greater mass results in high TSS.

Light Attenuation
   The attenuation of solar irradiance through a water column is measured by a dimensionless logarithmic function (k) per meter. The higher this light attenuation coefficient is, the more strongly light is attenuated (through absorbance or reflection) in the water column. Light attenuation ranged from 0.77 to 8.90 k/m and station annual means ranged from 1.69 to 4.08 k/m (Table 2.8). High light attenuation did not always coincide with high turbidity. Blackwater though low in turbidity may increase light attenuation. At NCF6 and BBT, blackwater stations with moderate turbidity levels, light attenuation was very high (Table 2.8). Light attenuation coefficients during this monitoring period were approximately equal to the five-year average at the river and estuarine stations (Figure 2.7). Temporally, light attenuation was highest after the hurricanes in late summer. This was similar to results after Hurricanes Fran and Bonnie, when light attenuation was highest system-wide because of flooding of highly colored swamp water into the main river channels (Mallin et al. 1999c). The high average light attenuation is a major reason why phytoplankton production in the major rivers and the estuary of the LCFR is generally low. Whether caused by turbidity or water color this attenuation tends to limit light availability to the phytoplankton.

Chemical Parameters - Nutrients

Ammonium
   
Ammonium concentrations ranged from 5 (detection limit) to 1110 m g/l and station annual means ranged from 38 to 258 m g/l (Table 2.9). Generally, the mean ammonium levels this monitoring period were higher than the five-year means at the channel stations (Figure 2.8). Areas with high ammonium levels this monitoring period included AC (mean = 148 m g/l), which is below a pulp mill discharge, LVC (mean = 258 mg/l), which may also be influenced by the pulp mill or from upstream industrial discharges. The stream sites with the highest levels of ammonium are mostly influenced by point source discharges. A peak in the middle estuary may be influenced by the City of Wilmington wastewater discharge and/or resuspension of sediment-bound ammonium at the turbidity maximum. Ocean dilution accounts for decreasing levels down into the estuary. The blackwater rivers had substantially higher ammonium levels during this monitoring period than the five-year means. ANC, although once a pristine site has apparently been influenced by logging activities. Another factor that may contribute toward increasing ammonium levels system-wide is airborne ammonium from the large number of concentrated animal operations (CAOs) in the basin.
    Temporally, lower ammonium usually occurs during colder months (Figure 2.9) , yet a winter peak in 1996 shows this pattern does not always hold up. Higher levels of oxygen in the water column will facilitate the conversion of ammonium to nitrate, and therefore during hot months with low oxygen, ammonium levels should be higher. The unpredictability of ammonium levels on a seasonal basis is likely due to the multitude of variables that may affect ammonium levels including input/sources, oxygen conditions, bacterial activity, and algal productivity.

Nitrate+Nitrite
   Nitrate+Nitrite (henceforth referred to as nitrate) is the main species of inorganic nitrogen in the Lower Cape Fear River. Concentrations ranged from 5 (detection limit) to 12,100 m g/l and station annual means ranged from 6 to 2,909 mg/l (Table 2.10). Station annual means for the 1998-99 monitoring period were similar to the five-year means (Figure 2.10). Highest nitrate levels at NC11 (mean = 617 mg/l) indicate that much of this nutrient is imported from upstream. Moving downstream from NC11, nitrate levels decrease, most likely as a result of uptake by primary producers and tidal dilution. The blackwater rivers carried low loads of nitrate compared to the mainstem Cape Fear stations, though the Northeast Cape Fear River (NCF117 mean = 308 mg/l) had higher nitrate than the Black River (B210 = 245 mg/l). No clear temporal pattern is observable for nitrate (Figure 2.11), although we can see the effects of Hurricanes Fran, Bonnie, and Floyd, as nitrate levels drop to very low levels. These drops may be a result of dilution and/or lack of oxygen, which would favor the ammonium nitrogen species over nitrate. A February 2000 peak (Fig. 2.11) was largely the result of unusually high nitrate concentrations at a number of locations (Table 2.10), particularly those draining numerous concentrated animal operations (CAOs). This may have resulted from mobilization of nitrogen deposited on floodplains during Hurricane Floyd, and carried into the streams during high January and February rains.
    Two stream stations, PB (mean = 1,198 mg/l) and BC117 (mean = 2,909 mg/l), carried extremely high levels of nitrate on several occasions, exceeding the North Carolina state drinking water standard of 10 mg/l twice. Both sites are strongly influenced by wastewater discharges upstream. Nitrate at several other tributary stations was noticeably elevated. Most of these stations are in the Northeast Cape Fear River watershed and may be influenced by agriculture and/or factory-style livestock operations, which can contribute high nutrient levels to local watersheds. High nitrate concentrations are becoming more common at SAR, an upper Northeast Cape Fear River station draining numerous hog farms (Table 2.10).

Total Kjeldahl Nitrogen
   
Total Kjeldahl Nitrogen (TKN) is a measure of the total concentration of organic nitrogen plus ammonium. TKN ranged from 71 to 2,060 mg/l and station annual means ranged from 377 to 1,201 mg/l (Table 2.11). Mean TKN for this monitoring period was lower than the five-year mean at all channel stations (Figure 2.12). Ammonium was generally higher for the channel stations this monitoring period and therefore organic nitrogen species must have been somewhat lower to account for low TKN. TKN concentration decreases down through the estuary, likely due to ocean dilution and food chain uptake of nitrogen. Measured TKN levels in the blackwater rivers are higher than in the mainstem Cape Fear River as a result of the high concentration of organic materials dissolved in the water (Figure 2.12). The stream stations typically have higher TKN as a result of the influence of swamp water with high organic and ammonium content. There is somewhat higher TKN during summer months (Figure 2.13). TKN has steadily declined at the Lower Cape Fear River channel stations over the five monitoring periods, 1995-2000.

Total Nitrogen
   
Total nitrogen (TN) ranged from 160 to 13,100 mg/l and station annual means ranged from 590 to 5,371 mg/l (Table 2.12). Mean total nitrogen was lower this monitoring period than for the five-year mean at all channel stations (Figure 2.14). Total nitrogen concentrations remained fairly constant down the river and declined into the lower estuary, most likely reflecting uptake of nitrogen into the food chain through algal productivity and grazing by planktivores as well as through dilution. The pulp mill above AC is a source of TN, increasing levels at this station over levels at NC11. The blackwater rivers carried total nitrogen loads somewhat lower than those found in the mainstem Cape Fear River (NCF117 mean = 1,037 mg/l, B210 mean = 847 mg/l). One stream station, BC117, had a very high mean of 5,371 mg/l, presumably from upstream wastewater discharge. Temporal patterns for TN are not evident (Figure 2.15), yet there is a conspicuous decline in TN in November 1997 to April 1998 minimum, followed by a gradual increase. A similar decline in TKN (Figure 2.13) and the lack of a decline in nitrate or ammonium suggests that the declining constituent of TN is organic nitrogen. Reasons for this trend are unknown.

Orthophosphate
   
Orthophosphate ranged from 1 to 2,940 mg/l and station annual means ranged from 9 to 721 mg/l (Table 2.13). The annual means at the channel stations this monitoring period were similar to the five-year means with some stations higher and some stations lower (Figure 2.16). Orthophosphate levels typically reach maximum concentrations during summertime (Figure 2.17), when anoxic sediment releases bound phosphorus. Also, in the Cape Fear River, summer algal productivity is limited by nitrogen, thereby allowing the accumulation of orthophosphate (Mallin et al. 1999a).
    A regression of summer orthophosphate for the previous monitoring period indicated that levels of this nutrient had slightly increased (Mallin net al. 1999b). Low orthophosphate concentrations after Hurricane Floyd helped to decrease the annual mean for the current monitoring period and the regression is not as strong (Figure 2.18). Much of the orthophosphate load is imported into the Lower Cape Fear system from upstream areas as NC11 typically has the highest levels. Yet during this monitoring period, the higher levels at AC suggests a source between the two stations, possibly the pulp mill upstream of AC. The Northeast Cape Fear River had higher orthophosphate levels than the Black River. Orthophosphate can bind to suspended materials and is transported downstream via turbidity, thus high levels of turbidity at the uppermost river stations may be an important factor in the high orthophosphate levels. Turbidity declines toward the estuary because of settling, and orthophosphate concentration also declines. In the estuary, primary productivity helps reduce orthophosphate concentrations by assimilation into biomass.
    BC117 (mean = 721 mg/l) had very high concentrations of orthophosphate and SAR (mean 158 mg/l), on the Northeast Cape Fear River, had moderately high orthophosphate levels. Although there is a textile discharge upstream, it is likely that the high number of factory-style livestock farms in the area contribute as a source of this nutrient.

Total Phosphorus
   
Total phosphorus (TP) concentrations ranged from 5 (detection limit) to 3,480 mg/l and station annual means ranged from 36 to 996 mg/l (Table 2.14). TP at the riverine channel stations down to NAV was lower this monitoring period than the five-year mean (Figure 2.19), while in the middle estuary TP was higher, and in the lower estuary it was lower. TP was higher than average in the Northeast Cape Fear River and lower than average in the Black River. TP was highest coming into the system at NC11 (mean = 172 mg/l) and declined into the estuary toward the ocean. Some of this decline is attributable to the settling of phosphorus-bearing turbidity, yet incorporation of phosphorus into the food chain is also responsible. TP can bind with turbidity and be transported downstream; these two parameters are positively correlated in the estuary (Mallin et al. 1999a). A temporal pattern of higher summertime TP (Figure 2.20) is a result of increasing orthophosphate as the spatial pattern of TP is similar to that of orthophosphate. At the stream stations BC117 (mean = 996 mg/l) exhibited high TP and SAR (mean = 293 mg/l) had moderate levels. Pickle plant discharge is likely the source of periodic high TP levels at NC403 (mean = 324 mg/l).

Organic versus Inorganic Nutrient Composition
 
  Organic nitrogen composition by station ranged from 46% to 75% of total N (Figure 2.21). The lowest levels were at NC11 (46%), increasing into the estuary at M54 (59%), and highest at the river mouth (75%). Organic nitrogen in blackwater rivers is naturally high (NCF117 = 72% and B210 = 73%) because of the complex dissolved compounds that drain from riparian swamps.
    The composition of phosphorus compounds (inorganic versus organic) was fairly constant at all stations, with organic phosphorus composition ranging from 56% to 67% of total P (Figure 2.22). In the Cape Fear River the lowest organic phosphorus composition was at NC11 (56%) with a gradual increase into the estuary at M54 (64%), and maximum percentages near the ocean at M18 (67%). Organic phosphorus composition was higher in the Black River (B210= 65%) than in the Northeast Cape Fear River (NCF117= 54%). Organic nitrogen percentages in the blackwater rivers were much higher than organic phosphorus (NCF117 - 72% vs. 54%, B210 - 73% vs. 65%). Higher ratios of organic versus inorganic compounds for both nitrogen and phosphorus in the estuary, along with higher algal biomass, reflect assimilation of nitrogen and phosphorus into the food chain via primary productivity.
    A clear temporal pattern is discernable for inorganic nitrogen to inorganic phosphorus ratios (Figure 2.23). The ratio is highest in late winter/spring, and during late summer dips below the Redfield ratio of 16:1 N:P. These ratios would theoretically lead to phosphorus limitation of primary productivity during the winter-spring period and nitrogen limitation in summer. Our experimental data demonstrate that summer nitrogen limitation does occur, but in winter primary production is light-limited (Mallin et al. 1999a). However, phosphorus limitation has been demonstrated experimentally in springtime (Mallin et al. 1999a).

Chemical Parameters - EPA Priority Pollutant Metals

    Aluminum levels in the Cape Fear system were generally high at NC11 and decreased downstream to NAV, where levels were again elevated (Table 2.15). Stream stations were generally low except for BC117, which is below the Burgaw Wastewater Treatment plant outfall (Table 2.15). 
    Arsenic, cadmium, and chromium all maintained concentrations below detection limits at all stations throughout the year (Tables 2.16, 2.17, and 2.18).
    Copper concentrations periodically exceeded the state tidal saltwater standard of 3 m g/L at some of the estuarine stations on occasion (Table 2.19). The freshwater standard of 7 m g/L was exceeded three times at BC117 (rating this station partially supporting) and twice at ROC, likewise rating it PS. Estuarine stations rated PS included NAV, HB, M54, M42 and M31.
    The LCFRP is an iron-rich system (Table 2.20). All of the freshwater stations except for NCF117 maintained average iron concentrations above the state standard of 1000 ug/L. Iron concentrations generally decreased down-estuary (Table 2.20).
    Water-column concentrations of lead and mercury were mostly below the analytical detection limit (Table 2.21, 2.22).
    Nickel concentrations exceeded the state standard twice at freshwater stations and exceeded the salt water standard once in the estuary (Table 2.23).
    Zinc concentrations remained below the state standard at all of the estuarine stations and most of the freshwater stations (Table 2.24). However, Station LRC exceeded the state standard once (Table 2.24).

Biological Parameters

Chlorophyll a
   During this monitoring period chlorophyll a was generally low at the river and estuarine stations of the LCFRP (Table 2.25; Figure 2.24). Production of chlorophyll a biomass is low to moderate in this system primarily because of light limitation by turbidity in the mainstem and high organic color and low inorganic nutrients in the blackwater rivers. Highest chlorophyll a concentrations are typically found during the period June through September (Fig. 2.25). During the past year chlorophyll a was lower than the long-term average, possibly a result of Hurricanes Dennis and Floyd causing extremely low levels September-November 1999 (Table 2.25; Figure 2.25). Spatially, highest values are normally found in the mid-to-lower estuary stations (Figure 2.24), because light becomes more available downstream of the estuarine turbidity maximum. Chlorophyll a production is extremely limited in the large blackwater rivers (Table 2.25; Figure 2.24).
    Substantial phytoplankton blooms do occur at the stream stations, particularly during summer months (see SR, PB, and GS - Table 2.25). These streams are generally shallow, so mixing does not carry phytoplankton cells down below the critical depth where respiration exceeds photosynthesis. Thus, when flow conditions permit, elevated nutrient conditions (such as are periodically found in these stream stations) can lead to algal blooms. In areas where the forest canopy opens up large blooms can readily occur. When blooms occur in blackwater stream stations, they can become sources of BOD upon death and decay, reducing further the low summer dissolved oxygen conditions common to these waters (Mallin et al. 1998b).

Biochemical Oxygen Demand
   Average five-day biochemical oxygen demand (BOD5) concentrations were approximately 1.0 mg/L at stations NC11, B210 and NCF117 (Table 2.26). Unexpectedly, average BOD5 and BOD20 were much less elevated at AC compared with NC11 compared with previous years (Mallin et al. 1999b), although several BOD20 were extremely higher at AC than at NC11. BOD displayed no discernable seasonal trend at any of the six stations (Table 2.26). There was not a major increase in BOD following Hurricane Floyd, contrary to what we have seen after other hurricanes (Mallin et al. 199b; 1999c). Sources for this BOD increase were swine waste inputs, malfunctioning human sewage systems, and increased non-point source contributions from swamp watersheds and agricultural areas. It is likely that dilution from the enormous amount of rainfall and wetland cleansing of the floodwaters may have helped reduce BOD increases.

Fecal Coliform Bacteria
   Fecal coliform (FC) bacterial counts in the LCFR system this monitoring period were lower than the five-year average at all stations. FC bacteria show a notable spatial trend of highest counts in the upper estuary-lower river area encompassed by NAV, HB, BRR, and M61 (Figure 2.26). The state human contact standard was exceeded twice, at AC and DP. The mainstem river stations otherwise display relatively low counts (Table 2.27). FC levels following Hurricane Floyd were unexpectedly low, consistent with other water quality parameters (Chapter 7).
    The stream stations that yield chronically elevated fecal coliform counts are mainly those downstream of point sources. LRC (below the site of the former Stevecoknit), BC 117 (below the Burgaw wastewater treatment plant), and BCRR all had geometric mean counts for the year exceeding the state standard for human contact of 200 CFU/100 mL (Table 2.27). BCRR had lower counts than BC117, but was also in violation of the health standard. As there are no major point sources listed upstream of BCRR, non-point sources may be responsible for these high counts. Based on the human contact standard of 200 CFU/100 ml, Stations N403, PB, LRC, BC117, BCRR, and HAM were non-supporting (NS). Stations LVC, GS, ROC, GCO, SR and BRN were partially supporting (Table 2.27).

 

2.4 - References Cited

APHA. 1995. Standard Methods for the Examination of Water and Wastewater, 19th ed. American Public Health Association, Washington, D.C.

Mallin, M.A., L.B. Cahoon, M.R. McIver, D.C. Parsons and G.C. Shank. 1997. Nutrient limitation and eutrophication potential in the Cape Fear and New River Estuaries. Report No. 313. Water Resources Research Institute of the University of North Carolina, Raleigh, N.C.

Mallin, M.A., M.H. Posey, M.L. Moser, G.C. Shank, M.R. McIver, T.D. Alphin, S.H. Ensign and J.R. Merritt. 1998a. Environmental Assessment of the Lower Cape Fear River System, 1997-1998. CMSR Report No. 98-02. Center for Marine Science Research, University of North Carolina at Wilmington, Wilmington, NC.

Mallin, M.A., L.B. Cahoon, D.C. Parsons and S.H. Ensign. 1998b. Effect of organic and inorganic nutrient loading on photosynthetic and heterotrophic plankton communities in blackwater rivers. Report No. 315. Water Resources Research Institute of the University of North Carolina, Raleigh, N.C.

Mallin, M.A., L.B. Cahoon, M.R. McIver, D.C. Parsons and G.C. Shank. 1999a. Alternation of factors limiting phytoplankton production in the Cape Fear Estuary. Estuaries 22:985-996.

Mallin, M.A., M.H. Posey, M.L. Moser, L.A. Leonard, T.D. Alphin, S.H. Ensign, M.R. McIver, G.C. Shank and J.F. Merritt. 1999b. Environmental Assessment of the Lower Cape Fear River System, 1998-1999. CMSR Report No. 99-01, Center for marine Science Research, University of North Carolina at Wilmington, Wilmington, N.C.

Mallin, M.A., M.H. Posey, G.C. Shank, M.R. McIver, S.H. Ensign and T.D. Alphin. 1999c. Hurricane effects on water quality and benthos in the Cape Fear Watershed: Natural and anthropogenic impacts. Ecological Applications 9:350-362.

U.S. EPA 1997. Methods for the Determination of Chemical Substances in Marine and Estuarine Environmental Matrices, 2nd Ed. EPA/600/R-97/072. National Exposure Research Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Cincinnati, Ohio.

Welschmeyer, N.A. 1994. Fluorometric analysis of chlorophyll a in the presence of chlorophyll b and phaeopigments. Limnology and Oceanography 39:1985-1993.

 

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