No *606r - UNT Digital Library/67531/metadc503963/m2/1/high_re… · This study encompassed approximately 35 km of the Red River between Shreveport and Natchitoches, Louisiana. The

THE EFFECTS OF PULP AND PAPER MILL WASTEWATERS

ON PHYTOPLANKTON PRIMARY PRODUCTIVITY IN

THE RED RIVER, LOUISIANA

THESIS

Presented to the Graduate Council of the

North Texas State University in Partial

Fulfillment of the Requirements

For the Degree of

MASTER OF SCIENCE

By

Jeffrey Dee Holler, B.S.

Denton, Texas

May, 1984

37'1

No *606r

Holler, Jeffrey, D., TbI Effects . LL; p d Paper Mill

Wastewaters gja Phytoplankton Primary Productivity in th Rad

River, Louisiana. Master of Science (Interdisciplinary

Studies), May, 1984, 108 pp., 36 tables, 10 figures,

bibliography, 29 titles.

Responses of phytoplankton productivity in the Red

River to unbleached pulp and paper mill wastewaters were

monitored using in situ 14C incubation. Preoperational

studies, conducted prior to the discharge of mill

wastewaters varied seasonally, but revealed similar

productivity trends when compared with postoperational

studies, conducted after mill discharges began entering the

Red River.

Carbon assimilation rates measured downstream of mill

discharge were generally greater than upstream levels in

both preoperational and postoperational studies.

Selected physical, chemical, and biological parameters

varied seasonally, but showed similar upstream-downstream

values and preoperational-postoperational values. Total

Organic Carbon (TOC), Dissolved Organic Carbon (DOC), and

Biochemical Oxygen Demand (BOD5) were positively correlated

with postoperational productivity rates. Apparent color was

negatively correlated with productivity rates.

TABLE OF CONTENTS

PageLIST OF TABLES . . . . . . * . . . . . . . . . . . . . v

LIST OF ILLUSTRATIONS . . . . . . . . . .!. . . . . .viii

Chapter

I. INTRODUCTION AND LITERATURE REVIEW . . . . .. 1

Mill DescriptionStudy AreaScope of StudyAn Overview of Primary ProductivityPaper IndustryPulp and Paper Mill Effluent CharacteristicsEffects of Pulp and Paper Mill Wastewater

on PhytoplanktonImportance of Total and Dissolved Organic

CarbonImportance of Adenosine Triphosphate

(ATP) and Chlorophyll aImportance of Biochemical Oxygen Demand and

Hydrogen Ion ConcentrationImportance of True and Apparent Color

Turbidity, and Suspended SolidsImportance of Nitrogen and PhosphorusImportance of LightDefinition of TermsObjectives and Hypotheses

II. MATERIALS AND METHODS . . . . . . . . . . . . 22

Productiqty StationsLa iitn C TudiesAnalysis of C Phytoplankton SamplesAnalysis of CarbonAnalysis of Adenosine Triphosphate (ATP)Light MeasurementsData Analysis

iii

III. RESULTS AND DISCUSSION . . . . . . . . . . . . 34

River and Wastewater FlowsIP Mansfield Mill Wastewater CharacteristicsPhytoplankton Primary ProductivityChlorophyll .TurbidityTotal Suspended SolidsAmmonium Nitrogen (NH3 -N)Nitrate Nitrogen (NO 3 -N)OrthophosphateTotal PhosphateTotal Organic CarbonDissolved Organic CarbonBiochemical Oxygen DemandTrue ColorApparent ColorAdenosine TriphosphateLightpHCorrelation of Physical/ChemicaL Parameters

with Phytoplankton Primary Productivity

IV. CONCLUSIONS . . . . . . . . . . . . . . . . * 101

BIBLIOGRAPHY . . . . . . . . . . . . . . . . . . . . . 106

iv

Chapter Page

LIST OF TABLES

Table Page

I. Physical, Chemical, and Biological WaterQuality Parameters Determined Monthlyat Selected Sampling Stations in theRed River . . . . . . . . . . . . . . . . . 6

II. Preoperational and Postoperational SamplingStation Locations on the Red River . . . . 24

III. Preopgratiogal Red River Mean Monthly Flows(m .sec ) for the Period November 1980Through August1981 . . . . . . . . . . 35

IV. Postoperational Red River Mean Monthly Flowsand IP Mansfield3Mill _ischarge Levels tothe Red River (m .sec ) for the PeriodOctober 1982 Through August 1983; Per CentDilution of Mill Effluent to Red RiverFlow . . . . . . . . . . . . . . . . . . . 36

V. IP Mansfield Mill Wastewater Effluent (WRR)Characteristics for the Period October 1982Through August 1983; Mean Values of ThreeReplicates; Units are mg/L for all ParametersExcept Turbidity (NTU), Color (CU),, ATP (ng/L);pH Values Were Determined with a Field Meterand Represent One Measurement per Survey. . 38

VI. Preoperational Red River Phytgplan ton 14CProductivity Rates-(mgC m .hr ). . . . . . 39

VII. Postoperational Red River Phy opla kton 14CProductivity Rates-(mgC m .hr ) . . . . . 47

VIII. Preoperational Red River PlagktonicChlorophyll a (mg.chlj.m ) . . . . . . . . 52

IX. Postoperational Red River P1 nktonicChlorophyll a (mg.chla.m ) . . . . . . . . 54

X. Preoperational Red River Turbidity (Nephelo-metric Turbidity Units) . . . . . . . . . . 55

XI. Postoperational Red River Turbidity (Nephelo-metric Turbidity Units) . . . . . . . . . . 56

V

Table Page

XII. Preoperational Red River Total Suspended Solids(mg/L) . . . . . . . . . . . . . . . . . . 58

XIII. Postoperational Red River Total SuspendedSolids (mg/L) . . . . . . . . . . . . . . . 59

XIV. Preoperational Red River Nitrate Nitrogen(mg/L) . . . . . . . . . . . . . . . . . . 61

XV. Postoperational Red River Nitrate Nitrogen(mg/L) . . . . . . . . . . . . . . . . .D . /6 3

XVI. Preoperational Red River OrthophosphatePhosphorus (mg/L) . . . . . . . . . . . . . 64

XVII. Preoperational Red River OrthophosphatePhosphorus (mg/L) . . . . . . . . . . . . . 67

XVIII. Preoperational Red River Total Acid HydrolyzablePhosphate Phosphorus (mg/L) . . . . . . . . 68

XIX. Postoperational Red River Total Acid HydrolyzablePhosphate Phosphorus (mg/L) . . . . . . . . 70

XX. Preoperational Red River Total Organic Carbon(mg/L) . . . . . . . . . . . . . . . . . . 71

XXI. Postoperational Red River Total Organic Carbon(mg/L) . . . . . . . . . . . . . . . . . . 73

XXII. Preoperational Red River Dissolved OrganicCarbon (mg/L) . . . . . . . . . . . . . . . 74

XXIII. Postoperational Red River Dissolved OrganicCarbon (mg/L) . . . . . . . . . . . . . . . 76

XXIV. Preoperational Red River Five-Day BiochemicalOxygen Demand (mg/L) . . . . . . . . . . 78

XXV. Postoperational Red River Five-Day BiochemicalOxygen Demand (mg/L) . . . . . . . . . . . 80

XXVI. Preoperational Red River True Color (ColorUnits) By Visual Method . . . . . . . . . . 81

XXVII. Postoperational Red River True Color (ColorUnits) By Visual Method . . . . . . . . . . 83

vi

XXVIII. Preoperational Red River Apparent Color (ColorUnits) By Visual Method . . . . . . . . . . 84

XXIX. Postoperational Red River Apparent Color (ColorUnits) By Visual Method . . . . . . . . . . 86

XXX. Preoperational Red River Adenosine Triphosphate(Nanograms/L) . . . . . . . . . . . . . . . 87

XXXI. Postoperational Red River Adenosine Triphosphate(Nanograms/L) . . . . . . . . . . . . . . . 89

XXXII. Total Light Energy Measured on the Red RiverDuring I iti Prirnry ProductivityExperiments (ly.hr ) . . . . . . . . . . . 91

XXXIII. Preoperational Red River Light Data for thePeriod November 1980 Through August 1981During La Situ Productivity Experiments;Surface Light (ft-c); Light at 1 Meter(ft-c); Vertical Absorption Coefficient(k) . . . . . . . . . . . . . . . . . . . . 93

XXXIV. Postoperational Red River Light Data for thePeriod November 1982 Through August 1983During a tu Productivity Experiments;Surface Light (ft-c); Light at 1 Meter(ft-c); Vertical Absorption Coefficient(k) . . . . . . . . . . . . . . . . . . . . 95

XXXV. Preoperational Red River pH Values; SingleMeasurements Determined in the Field with aPortable pH Meter . . . . . . . . . . . . . 98

XXXVI. Postoperational Red River pH Values; SingleMeasurements Determined in the Field with aPortable pH Meter . ... .. . . . . . . .99

vii

Table Page

LIST OF ILLUSTRATIONS

Figure

I. Location of the International Paper Mansfield,Louisiana Mill in Relation to SurroundingCities and Parishes . . . . . . . . . . "

2. Map of the Bayou Pierre and Red River SamplingStations . . . . . . . . . . . " . . . .

3. PhytoplanktonRed River,








Primary Productivity Data forNovember 1980 . . . . . ...

Primary Productivity Data forFebruary1981 . . . . . . . .

Primary Productivity Data forMay 1981 . . . . . . . . .

Primary Productivity Data forAugust 1981 . . . . . . .

Primary Productivity Data forNovember 1982 . . . . . . .

Primary Productivity Data forFebruary 1983 . . . . . . .

Primary Productivity Data forMay 1983 . . . . . . . . .

Primary Productivity Data forAugust 1983 . . . . . . . .

viii

Page

2

4

41

42

43

44

48

49

50

51

."

.

"

."

CHAPTER I

INTRODUCTION AND LITERATURE REVIEW

The purpose of this research was to evaluate the impact

of treated wastewaters discharged from International Paper

Company's (IP) Mansfield, Louisiana mill on phytoplankton

primary productivity in the Red River. A preoperational

baseline of chemical, physical, and biological data were

developed by the Institute of Applied Sciences (IAS) at

North Texas State University prior to mill start-up (12).

Primary productivity measurements obtained in the

preoperational study were compared with parallel

measurements taken in this postoperational study conducted

after mill start-up. Comparisons were made to determine

what effects, if any, discharged paper mill wastewaters have

had on phytoplankton primary production in the Red River.

Mill Description

The Mansfield Mill, located in Desoto Parish, Louisiana

approximately 48 km southeast of Shreveport, Louisiana,

processes pulp and wood chips to produce containerboard.

Limited operations began in November, 1981. Figure 1 shows

the mill location in relation to the Red River.

1

2

t1

ARKANSASI#

TEXAS *LOUISIAN l WEBSTER CLAIBORNE +I

\PARISH PARSH

* OSSIER }! 4PARISH I- )

-. ,

CADDO me i MINDEPARtSH\

\ t \.

BOSSIER 1-2o -- -- - -- ----CITYII

SHREVEPORT I RITO

C INI E

-_ PARISH

MA NSFIELD -- --"MILL \'RED A--.R

PARISH \CLEAR LAXE ..I ........._ .....-.-....-.

S /THr*ORT LAKE J}t}\

DE SOTOu5 yPARtSH

LMANSFIELD

NATCH TOCHES

\ . ! PARISH

\ - -SABINEPARISH;r

\ NATCHITOCHES

ALEXANDRA'

0 5 10 20Mi. <

S A EL

E VLEFig

. -- Location of the I. P . Mansfield

, LA

Mill in relation to surrounding cities and parishes.

3

The mill's wastewater discharge consists of a mixture

of treated process wastewaters, treated sanitary wastewaters

and storm water runoff. The combined wastewaters receive

primary clarification and secondary treatment by spray

application to a 600-acre overland flow facility. The total

combined wastewaters are generated at an approximate rate of

12,112 m3 day~ (3).

Study Area

This study encompassed approximately 35 km of the Red

River between Shreveport and Natchitoches, Louisiana. The

study area extended from 1.6 km north of Abington to 11.3 km

downstream of the IP pipeline discharge site. (See Figure

2.) Wastewaters are discharged midway between stations 1RR

and 2RR.

In this area, the Red River is a wide, shallow,

meandering river with a sand substrate. Flow rates in the

river are highly variable, ranging from 396 m3'sec~ 1 to as

high as 36,576 m3.sec~ (21). The majority of land in the

study area is used for agricultural purposes. However, much

of the land next to the river is forested.

Scope of Study

The study was conducted in accordance with the

preoperational study design. Preoperational in situ

phytoplankton primary productivity experiments were

conducted on a quarterly basis during November 1980 and

4

Howard

P 0--

4

Mansfield

WOP

I M Overflow Outfo.P Mill OutfallRRW

A ington

SA

S608 RtM23

Coushatta

0 1 2 3 4 Smiles

LR Evelyn RE

r Jordon Ferry Bridge

Fig. 2--Map of the Bayou Pierre and Red River samplingstations.

5

February, May, and August, 1981. Similarly, the

postoperational in situ productivity experiments were

carried out in November 1982 and February, May, and August,

1983. Monthly triplicate water samples were collected and

returned to IAS laboratories for analysis of all other

physical/chemical water quality parameters studied. The

period from November 1980 through August 1981 was selected

from preoperational studies for comparison with the

postoperational studies being conducted from October 1982

through August 1983. Physical, chemical, and biological

water quality parameters analyzed are listed in Table I.

An Overview of Primary Productivity

This study was designed to assess the impact of mill

wastewaters on in situ phytoplankton primary productivity.

Because paper mill wastewaters are typically high in color,

primary productivity studies were conducted to assess the

possible effects on phytoplankton. A reduction in

photosynthesis would be expected provided increased light

attenuation occurred in the Red River from discharged

wastewaters. Research conducted in coastal waters of

British Columbia has shown that light attenuation and

selective absorption of 400-500 nm wavelength light by paper

mill wastewaters were the major factors responsible for

reduced primary productivity in the zone of influence. In

6

TABLE I

PHYSICAL, CHEMICAL, AND BIOLOGICAL WATER QUALITY PARAMETERSDETERMINED MONTHLY AT SELECTED SAMPLING

STATIONS IN THE RED RIVER

PARAMETER METHOD REFERENCE

TOC

DOC

BOD

NO 3 -N

NH3 --N

Ortho PO-P

Total PO~P

LightPenetration;

Color,Apparent

Color, True

Chlorophyll

ATP

Turbidity

SuspendedSolids

Combustion-IR Detection

Combustion-IR Detection

Incubation, 5 days

Corning Meter

Orion Electrode

Orion Electrode

Ascorbic Acid

Digestion-Ascorbic Acid

Protomatic Meter

Visual Comparison

Visual Comparison

Spectrophotometric

Bioluminesence

Nephelometric

Evaporation

Standard Methods

Standard Methods

Standard Methods

p.471

p.471

p.483

Standard Methods p.369



Standard Methods p.6 1





Parameters underlined were determined in the field.All other parameters were analyzed in the IAS laboratoriesin Denton, Texas.

7

addition, phytotoxicity occurred only at high concentrations

of waste mill wastewaters (18).

The role of autotrophic phytoplanktonic productivity

within an aquatic ecosystem stems from the synthesis of

organic substances from inorganic raw materials acting as

electron donors. This process can be summarized by the

universally-known photosynthesis equation:

6C0 + 12 H20 Light } C H 0 + 6H 0 + 602 2 Pigment 6H12 6 2 2Receptor

The use of inorganic reductants is termed lithography.

This process can be categorized as either chemosynthetic,

carried out by chemosynthetic bacteria or photolithotrophic,

carried out by photosinthesizing plants (1). Both processes

require a source of energy and a usable source of inorganic

carbon. This study is concerned only with photolithotropic

planktonic organisms of the aquatic assemblage.

Techniques used to measure direct rates of in situ

primary productivity have received much attention in recent

years. Specifically, radioactive1C tracer techniques have

been used as a highly sensitive measure of primary

productivity (17; 19; 22). The total carbon assimilated in

photosynthetic processes can be determined through the

addition of a known amount of radioactive tracer

8

NaH1 4 Co3 into the organic matter of phytoplankton. The

amount assimilated can then be measured by liquid

scintillation counting techniques. The uptake of NaH 4CO3

has been shown to estimate the assimilation of total

inorganic carbon, which is an estimate of the rate of

primary production in mgC.m-3.hr-1 (23).

Paper Industry

The paper industry depends upon wood fiber as a

paramount natural resource. The United States, with only 6

per cent of the world's population, uses 33 per cent of the

world's energy and natural resources (14). Per capita

consumption of paper and paper products in this country

reached approximately 295 kg per year in 1978, and is

expected to reach 454 kg per year in the next generation.

With the present demand for pulp and paper products, it is

possible to consume more trees than natural regrowth will

accommodate (14).

An adequate supply of high quality water is a necessary

raw material in the paper industry. Several key properties

of water affect the paper making process. Ideal water

should be free of excessive suspended materials, possess

little color, have an absence of iron, magnesium, and

silica, have neutral pH, and have a uniform temperature.

Suspended matter causes spots and imperfections in paper due

to capillary attraction by the fibers. Color influences

9

brightness and the amount of color permissible depends on

the quality of paper products desired (14).

Iron and magnesium compounds tend to be absorbed to

cellulose, resulting in a yellowing of the fibers (in the

case of bleached and white grades of paper). These

compounds also cause paper to deteriorate when exposed to

light. Other dissolved minerals, such as copper and

sulphur, affect the brightness of paper. The presence of

silica presents scaling problems in boilers and condensers,

reducing operating efficiency.

Pulp and Paper Mill Effluent Characteristics

Effluent is defined as any liquid or liquid-containing

solids in suspension which is emitted from any premises in

the form of waste (5). General paper mill effluents

comprise any of the following combinations:

1. Suspended matter, which includes loading materialssuch as clay, titanium pigments and coloringagents, together with fibers;

2. Other process waste, such as fibers, sizingchemicals and coating waste, together withlaboratory and general trade wastes.

Water reuse diminishes the quantity of fresh water

used. Treatment remedies employed to recover chemicals,

fibers, and water resources include

1. Floatation, which relies on the principal of abalanced air content in the water;,

2. Mechanical filtration, in the form of drums anddisc filters, pressure filters, as well as sandand micro-filters;

10

3. Biochemical treatment methods which includeanaerobic and aerobic treatment technologies;examples of such technologies include activatedsludge systems, trickling filters, lagoons andstabilization basins, as well as overland flowsystems.

The overland flow treatment technology employed at the

International Paper Company's Mansfield mill reduces the

waste load prior to discharge into the Red River. Mill

wastewater is sprayed through fine mister nozzles, and is

collected after percolation to a sealed layer of soil.

Surface runoff is also collected and discharged along with

treated wastewaters via a pipeline into the Red River. This

process provides aerobic decomposition of wastes, removing a

large portion of the oxygen demanding potential of the

untreated paper mill wastewaters.

Effects of Pulp and Paper MillWastewater on Phytoplankton

Phytoplankton organisms provide the basis of many

aquatic food chains. Constituents of the wastewaters may

inhibit their growth, reducing the production of an entire

community (13). Pulp and paper. mill wastewaters can affect

aquatic organisms due to increasing suspended solids and

color in the water column, resulting in increased light

attenuation. This indirect effect can diminish the

photosynthetic capabilities of phytoplankton organisms (18).

In addition, these paper mill wastewaters are typically high

in oxygen-consuming materials (8). Therefore, the

11

degredation of aquatic systems may also occur through the

removal of dissolved oxygen in some local conditions.

Pulp and paper wastewaters can contain a number of

toxic substances, such as chlorinated phenols, sulfides,

mercaptans, resins, and fatty acids. These substances may

have an effect on phytoplankton productivity, zooplankton,

and fish. Laboratory experiments have shown that filtering

rates Daphnia retrocurva were decreased when exposed to 5

per cent and 10 per cent solutions of raw pulp and paper

mill wastewaters (2). Further studies in Nipigon Bay, Lake

Superior, have indicated changes in the fish community

exposures to pulp and paper mill wastewaters. It was

determined that these changes occurred as a result of

short-term responses of fish to the wastewaters, as well as

long-term alteration in environment, both acting in concert

(9).

Importance of Total and Dissolved Organic Carbon

Total organic carbon (TOC) is a gross expression of the

organic chemical content of waters and wastewaters (16). As

such, TOC can be used to monitor processes for the treatment

or removal of organic contaminants. Therefore, TOC

measurements can provide information concerning the impact

of pulp and paper mill wastewaters on overall water quality

in the Red River. Pulp and paper mill wastewaters have been

12

characterized as having a high potential input of

oxygen-consuming materials into the aquatic environment (8).

The input of dissolved organic carbon (DOC) into a

receiving stream from pulp and paper mill wastewaters is

known to affect light attenuation by both scattering and

absorptive mechanisms (7). These mechanisms may affect

light attenuation in the Red River, provided discharged mill

wastewaters contain a greater DOC content than receiving

waters. A reduction in photosynthetic capabilities of

phytoplankton organisms has been shown to be avoided by

mixing and dilution of the paper mill wastewaters (10).

Importance of Adenosine Triphosphate(ATP) and Chlorophyll a

Adenosine triphosphate measurements can be used as an

indication of total microbial biomass and chlorophyll a

determinations can provide information about

photosynthesizing plant matter. Estimations of biomass

using ATP determinations can be made. All living cells,

whether plant or animal, contain ATP. Furthermore, it is

assumed that ATP is not associated with nonliving

particulate material, and that the ratio of ATP to cell

carbon remains fairly constant. Previous studies have shown

that biomass calculations based on ATP and chlorophyll -

determination were in agreement with those calculated by

direct measurement (6).

13

Chlorophyll g. can also be used as an indicator of algal

biomass and constitutes, on the average, 1.5 per cent of the

dry organic matter (ash-free dry weight). An estimation of

algal biomass is obtained when the chlorophyll a value is

multiplied by a factor of 67 (16).

Importance of Biochemical Oxygen Demandand Hydrogen Ion Concentration

Previous studies have documented the oxygen-consuming

characteristics of pulp and paper mill wastewaters (8, 15).

Assuming that the wastewaters entering the Red River contain

an oxygen-demanding substance which adversely affects

dissolved oxygen concentrations downstream from the

discharge site, phytoplankton production may be adversely

affected in the Red River. Dilution of the wastewater

discharge may act to offset the oxygen demand, as well as to

contribute to spatial and temporal decomposition.

The pH is defined as the logarithm of the reciprocal of

the free hydrogen ions (23). The "p" of pH refers to the

power (puissance) of the hydrogen ion activity. Acidic

waters possess greater hydrogen ion concentrations, while

alkaline waters contain fewer. A pH value of 7.0 is

neutral, neither acidic nor alkaline. Values below 7.0 are

acidic, while those above 7.0 are alkaline. The hydrogen

ion concentration, as measured by pH, can play a key role in

determination of toxicity of pulp and paper mill wastewaters

to aquatic phytoplankton. Moore and Love (11) found that a

14

reduction in the carbon uptake by phytoplankton was due to

effluent pH.

Importance of True and Apparent ColorTurbidity, and Suspended Solids

True and apparent color, turbidity, and total suspended

solids (TSS) are all known to affect light attenuation by

both scattering and absorption mechanisms, and would be

expected to have an influence on phytoplankton productivity

in the Red River (23). Alterations in the values of these

parameters in the Red River as a result of discharged

wastewaters may be reflected in changes in primary

productivity. Provided the wastewaters cause increased

light attenuation in the water column, a decreased level of

phytoplankton productivity would be expected. Less light

would be available to phytoplankton organisms. This

relationship would be true primarily during normal light

conditions. However, at extremely low or high light

conditions a decrease in photosynthetic processes, due to

decreased light, would not be proportional.

Importance of Nitrogen and Phosphorus

Nitrogen compounds have been shown to be important in

algal productivity (22). Phosphorus and phosphorus cycling

rates are the most frequent regulating mechanisms of primary

productivity (23). Therefore, it is imperative that

nitrogen and phosphorus compounds be considered in an

15

assessment of primary productivity in the Red River. These

vital nutrients serve as the base of phytoplankton

production, and any production changes resulting from mill

wastewaters would be reflected in either increased or

decreased phytoplankton populations or rates of

photosynthesis.

Importance of Light

As a means of relating possible alterations in water

quality resulting from mill wastewater discharges,

measurements of the amount of light energy impinging on the

water column were made. It is apparent from the general

photosynthetic formula that the amount and character of

light entering the aquatic system has much to do with

primary production levels of phytoplankton organisms.

Light absorption, or attenuation coefficients, can be

calculated to describe the rate at which various wavelengths

of light disappear through the water column (4; 20; 22).

Vertical absorption coefficients are expressed as:

k = n Io - In Iz

z

where:

k = vertical absorption coefficient

z = depth (m)

I = subsurface irradiance

Iz = irradiance at depth, z (1).

16

Surface light intensity readings were made to determine

the incident light. In addition, readings were taken at one

meter, or off the bottom if the water depth was less than

one meter. It was possible from these two measurements to

calculate the vertical absorption coefficients at each

sampling station (lRR-4RR).

Definition of Terms

1. Primary Productivity is defined as the rate at

which radiant energy is stored by photosynthetic and

chemosynthetic producer organisms in the form of organic

substances.

2. Gross Primary Productivity is defined as the total

rate of observed change in biomass, plus all predatory and

nonpredatory losses divided by the time interval.

3. Net Primary Productivity is defined as the gross

rate of accumulation or production of new organic matter or

stored energy, less losses, divided by the time interval.

4. Standing Crop is defined as the weight of organic

material that can be sampled or harvested by normal methods

at any one time from a given area or volume.

5. Biomass is defined as the weight of all living

material in a unit area at a given instantaneous time.

17

6. Production is defined as the weight of new organic

material formed over a period of time, plus any losses

during that period.

Objectives and Hypotheses

The objectives of this study were to assess the impact

of wastewaters from International Paper Company's paper mill

on in sit.u primary productivity in the Red River and to

determine whether there was any significant difference (p$

0.05) between the upstream reference site (station 1RR) and

downstream experimental sites (stations 2RR, 3RR, and 4RR).

A second objective was to compare the postoperational data

on in situ primary productivity with the previously

collected preoperational data.

To accomplish these objectives, primary productivity

was measured in the field and associated water quality

parameters were determined in the laboratory. Primary

productivity values obtained at the upstream reference site

were compared with downstream experimental site values to

determine possible effects of the mill wastewaters on

phytoplankton productivity in the Red River. Likewise,

water quality parameters potentially influencing primary

productivity were analyzed between upstream reference and

downstream experimental sites to isolate possible factors

influencing resultant differences in primary productivity of

the phytoplankton organisms.

18

The following hypotheses indicate two possible results

of upstream reference site versus downstream experimental

site comparisons:

1. H0 : Phytoplankton primary productivity was not

altered at downstream experimental sites relative to

upstream reference site.

H : Phytoplankton primary productivity was altered

at downstream experimental sites relative to upstream

reference site.

2. H0: Physical, chemical, and biological water

quality parameters associated with primary productivity were

not altered at downstream experimental sites relative to


H : Physical, chemical, and biological waterHa

quality parameters associated with primary productivity were

altered at downstream experimental sites relative to


CHAPTER BIBLIOGRAPHY

1. Cole, G. E. Textbook Qf Li nolo.. gy, St. Louis, C. V.Mosby Company, 1979.

2. Cooley, J. M. 1977. Filtering rate performance ofDaphnia retrocura in pulp mill effluent.i. Fish. Res. d. .a . 34: 863-868.

3. Engineering Science, Inc., 1979. Environmentalassessment for .t IP-1. c oia nerboard

complex, Desoto Parish, Louisiana. FinalReport to International Paper Company,Mansfield, Louisiana.

4. Gotterman, H. T. Physiological Limnology, New York,Elsevier Scientific Publishing Company, 1975.

5. Higham, R. R. A. A Handbook QI Papermaking, OxfordUniversity Press, London, 1968.

6. Holm-Hansen, 0. and R. Booth. 1966. The measurementof ATP in the ocean and its ecologicalsignificance. Limnil. and Oceanogr.11: 510-519.

7. Hutchins, F. E. The Toxicity of Pulp and Paper MillEffluent: A Literature Review. EPA-600/3-79-013 Environmental Research Laboratory, Corvallis,OR., 1979.

8. Johnson, M. G. 1977. Caloric changes along pulp andpaper mill effluent plumes. . Fsh Bd.Can. 34: 784-790.

9. Kelso, J. R. M. 1977. Density, distribution, andmovement of Nipigon Bay fishes in relation to apulp and paper mill effluent. J. Fish. Res. Bd.Can. 34: 879-885.

10. Minns, C. K. 1977. Analysis of a pulp and paper millplume. T. Fish. Res. Bd. .Can. 34: 776.

19

20

11. Moore, J. E. and R. J. Love. 1977. Effect of pulpand paper mill effluent on the productivity ofperiphyton and phytoplankton. J. Fish. Res.Bd. Can. 34: 856.

12. Preoperational Aquatic Studies at the Mansfield Mills,Volume 2: Baseline Report. May 1982. Instituteof Applied Sciences, North Texas StateUniversity, Denton, Texas.

13. Rainville, R. P., B. J. Copeland, and W. T. McKean.1975. Toxicity of Kraft mill wastes to anestuarine phytoplankter. J. Water Poll. Count.Fed. 47: 487-503.

14. Saltman, David. Paper si. New York,Van Nostrand Reinhold Company, 1978.

15. Sibert, J. and R. R. Parker. 1973. Effect of pulpmill effluent on dissolved oxygen in a stratifiedestuary, II Numerical Model. Water Res.7: 515-523.

16. Standard Methods for the Examination of Water andWastewater, 15th ed., APHA-AWWA-WPCF, AmericanPublic Health Association, 1980.

17. Steeman-Neilsj, E. 1952. The use of radioactivecarbon ( C) for measuring organic productionin the sea. 2. Cons. Internat. Explor. Mer.18: 117-140.

18. Stockner, J. G. and David D. Cliff. 1976. Effects ofpulp mill effluent on phytoplankton production incoastal marine waters of British Columbia.T. Fish. Res. Bd. Con. 33: 2422-2433.

19. Strickland, J. D. H. 1960. Measuring the productionof marine phytoplankton. Bull. Fish. Res. Bd.Con. 122: 172.

20. Talling, J. F. 1957. Photosynthetic characteristicsof some freshwater plankton diatoms in relationto underwater radiation. New Phytol. 56:29-50.

21

21. United States Geological Survey, 1978 - 1981. Waterresources data for Louisiana Vol. I., Central andNorthern Louisiana. Water years 1978, 1979,1980, and 1981. Water Resources Division,U. S. G. S., Jonesboro, LA.

22. Vollenweider, R. A. A Saul f Methods fQLMeasurig Primary Production in AquaticEnvironments, 2nd ed., London, Blackwell, 1974.

23. Wetzel, R. G. Limnology. Philadelphia, W. B.Saunders Company., 1975.

CHAPTER II

MATERIALS AND METHODS

Preoperational productivity experiments were conducted

on the Red River in November 1980 and in February, May, and

August, 1981. Postoperational productivity experiments were

conducted in November 1982 and in February, May, and August,

1983. These studies were in situ experiments. All other

water quality parameters were sampled on a monthly basis

throughout this entire sampling period, and were analyzed in

the Limnology laboratories at North Texas State University.

Productivity Stations

Sampling stations were chosen for primary productivity

experiments as shown in Figure 2 in Chapter I. Station 1RR

is located 1.6 km upstream of the International Paper (IP)

outfall to the Red River. This station was chosen as a

reference site to represent river conditions unaffected by

paper mill effluents. Three additional sampling stations

were distributed downstream from the IP pipeline discharge

site. These stations were designated 2RR, 3RR, and 4RR and

were located 1.6 km, 4.8 km, and 11.3 km, respectively,

downstream from the IP outfall. one additional station,

WRR, was chosen at the point where mill wastewaters enter a

pipeline connected to the outfall. Station WRR was

22

23

monitored for chemical parameters only. Sampling station

descriptions are presented in Table II.

In Situ 14C Studies

The classic light and dark bottle 14 C method (5) of

measuring planktonic productivity was performed at each

sampling station (excluding WRR). Triplicate, 300 ml,

Wheaton light and dark bottles were filled at the respective

stations with river water and inoculated with 1 ml of 14C

labeled sodium bicarbonate solution (Na14CO3). The bottles

were incubated in a floating incubation rack for a

photo-period of approximately four hours. Incubation depth

for the bottles ranged from 5 to 10 cm.

One incubation bottle marked "field standard" was

filled with sample water at both upstream (IRR or 2RR) and

downstream (3RR or 4RR) locations by one of two field crews.

These bottles were injected with 1 ml of 14C labeled sodium

bicarbonate solution, shaken, and 5 mls of the solution was

placed into a scintillation vial containing 15 mls of

Aquasol-II (New England Nuclear) scintillation fluid. This

mixture was shaken and placed in the field box for shipment

back to the laboratory. This sample was used to determine

how much 4C was actually inoculated into the light and

dark bottles in the field. Field standard incubation

bottles were not acidified prior to injection of 5 ml

subsamples into the scintillation vials.

24

TABLE II

PREOPERATIONAL AND POSTOPERATIONALSAMPLING STATION LOCATIONS

ON THE RED RIVER

Station Description P 0Number

1RR 1.6 km upstream of the IP* pipe-line discharge site on the RedRiver (near Abington, La) X X

2RR 1.6 km downstream of the IP*pipeline discharge site on theRed River (near Abington, La) X X

3RR 4.8 km downstream of the IP*pipeline discharge site on theRed River X X

4RR 11.3 km downstream of the IP*pipeline discharge site on theRed River (8 km upstream ofCoushatta, La) X X

WRR Overland flow wastewater at thepermit point X

P = Preoperational; 0 = Postoperational;* = International Paper Company.

25

One ml of 3N H2SO4 was injected into each phytoplankton

bottle at the end of the incubation period to terminate the

14C experiments. The acid acted to halt the photosynthetic

reactions and also served to convert the unassimilated

inorganic carbon, both radioactive and normal isotopic, to

free CO2 by lowering the pH to less than 2.0. Bubbling the

subsamples with air, as described later, drives off the

gaseous 14CO2 and 1 2 CO2, leaving only the 1 4 C bound as

organic compounds for liquid scintillation assay (3).

Analysis of 14 C Phytoplankton Samples

Assimilation of 14C by phytoplankton was determined by

liquid scintillation counting techniques. In the

laboratory, the phytoplankton incubation bottles were shaken

twenty to twenty-five times to assure sample uniformity. A

5 ml subsample was then removed from each bottle and placed

into a scintillation vial. The scintillation vial was then

placed in a vacuum bubbling chamber. The chamber top was

liberally greased with stopcock grease and clamped down to

the bottom with four wing-nuts (one per corner). Pasteur

pipets were fitted through the openings in the top,

extending down into the 5 ml subsample. Vacuum was applied

to the chamber and adjusted until each vial was bubbling

approximately at the same rate. Subsamples were allowed to

bubble for 20 to 30 minutes. Vial caps were labeled with

26

the appropriate station number and replicate letter while

subsamples were bubbling.

Subsample vials were removed from the chamber after

bubbling and 15 mls of Aquasol-II (New England Nuclear) was

added to each vial before capping. Each vial was wiped

clean of finger prints and/or other contaminants and then

placed in a Beckman LS-l00-liquid scintillation counter.

Subsamples were allowed to sit overnight (dark adapt) to

quench chemical and/or light-stimulated scintillations prior

to counting.

The subsamples were then counted three times each for

one minute using channel 2 (C-14 + 3H) with a preset error

of 0.2 per cent. Three 14C-toluene standards (New England

Nuclear) containing 25,625 disintegrations per minute (dpm),

52,500 dpm, and 102,500 dpm were counted along with the

plankton subsamples to determine counting efficiency for

each respective count. The percentage of disintegrations

per minute counted relative to the known quantity in the

standards were used to determine counting efficiencies.

Absolute phytoplankton productivity rates were calculated

from the following equation (4, modified):

Phytoplankton 14C x C12.x.064Productivity =

1C. x T

where:

14Cf = (cpm light-cpm dark) x 10 3 ml.L-1

12Ci = initial dissolved inorganic carbon (mgC.L1 )

27

14C. = C initially available (cpm)

T = incubation time (hr)

1.064 = isotopic correction factor for 1 4 C (6).

Analysis of Carbon

Field

Triplicate prewashed 25 ml glass sample vials were

filled with river water at all Red River sampling stations.

The samples were stored on ice and returned to the

laboratory for analyses.

Laboratory

A Beckman Model 915 Total Organic Carbon analyzer was

coupled with a Beckman Model 215-A Infrared analyzer for

carbon analyses. A Perkin-Elmer Model 056 chart recorder

was employed to record peak heights. The TOC analyzer

consists of two channels, inorganic and total. It was

necessary to warm up both channels prior to sample injection

by turning on the ovens approximately one hour before

analysis. The total inorganic carbon channel was operated

at 150*C and the total organic carbon channel operating

temperature was 950*C. A carrier gas of nitrogen was

utilized at a flow rate to each oven of 150 mls.min~1.

Inorganic carbon standards were prepared according to

the procedures described in the Beckman TOC analyzer

instruction manual. This procedure involved dissolving

28

4.404 gm anhydrous sodium carbonate in 500 mis of C0 2-free

water in a 1-liter volumetric flask. Also, 3.497 gm

anhydrous sodium bicarbonate was added to the flask and

diluted to one liter with C0 2-free water. This solution

contained 1000 ppm inorganic carbon. Working standards were

prepared by adding 1, 2, and 3 ml of the 1000 ppm stock

solution to separate 100 ml volumetric flasks and diluting

to 100 mIs with C02 -free water. These working standards

contained inorganic carbon concentrations of 10, 20, and 30

ppm, respectively.

After warm-up procedures were accomplished, a 200 i1

subsample of each working standard was injected into each

channel for the purpose of obtaining data to develop a

standard curve. Next, sample vials were shaken and 200 uls

portions were drawn with a special syringe and injected into

both channels. As the 200 ul portion of sample entered the

heated-packed column, vaporization occurred and the organic

matter was oxidized to carbon dioxide. The amount of carbon

dioxide generated was measured by means of the infrared

analyzer and recorded on chart paper by the chart recorder.

After raw samples were injected into both channels, a

portion of raw sample was then filtered through a 0.45 um

glass fiber filter. The filtrate was then injected into

both channels, as previously described. These injections

yielded inorganic and total carbon data for dissolved

29

carbon. Absolute TOC and DOC sample concentrations

(mgC.L-1) were calculated from the following equations:

TOC = unfiltered TC - unfiltered IC

DOC = filtered TC - filtered IC

where:

TC = total carbon channel

IC = inorganic carbon channel.

Analysis of Adenosine Triphosphate (ATP)

ATP analysis was performed on all triplicate Red River

samples following each monthly survey. A subsample of 10 to

50 mIs of wastewater was filtered through a sterile 0.45 um

filter using vacuum at 12 to 15 mm Hg. Immediately prior to

the filter being sucked dry, the vacuum was turned off and

the filter was placed face down in boiling Mclllvaine buffer

solution (1). Mclllvaine buffer is a sodium

phosphate/citrate buffer with an adjusted pH of 7.70.

Filters were then extracted for three minutes, removed

and rinsed with sterile boiling buffer. The solution was

allowed to continue extracting for an additional two

minutes. The final extract was diluted to 10 mls in a

graduated cylinder, transferred to a labeled test tube and

frozen until assayed.

To perform ATP assays, 250 mg of firefly lantern

extract was rehydrated in 25 mls of deionized water. The

firefly lantern extract was allowed to stand at ambient room

30

temperature for 2 to 3 hours, at which time it was

centrifuged at 4000 rpm for 20 minutes. The supernate was

decanted and allowed to stand an additional 18 to 20 hours

at ambient room temperature. It was necessary to age the

firefly enzyme for this period of time in order to decrease

its background for best reproducibility.

A SAI Technology Model 2000 ATP photometer was used to

assay extracted samples. Frozen samples were removed from

the freezer and allowed to thaw to room temperature before

being analyzed. Stock ATP standards were prepared prior to

analyses and frozen. Stock ATP standards contained 100

ng.mL-1 and were diluted to working concentrations ranging

from 0.625 to 10 ng.L-1 for development of a standard curve.

Assay procedures involved the addition of 200 Is of

sample or standard to a glass scintillation vial. Next, 200

Is of aged firefly enzyme was injected into the vial and

swirled to insure adequate mixing. The vial was placed into

the photometer, which had began a 15-second delay sequence

upon enzyme and sample introduction. Counts were made in a

60-second integrated mode and recorded. Final ATP

concentrations (ng.L-1) were calculated from the

predetermined standard curves.

31

Light Measurements

To identify possible light attenuation in the water

column resulting from mill wastewaters, measurements of the

amount of light energy impinging on the experimental

stations during each monthly survey were made. This was

accomplished using two light measurement instruments. A

portable Belfort 5-3850 pyranograph measured the total light

energy ranging from 280 to 2000 nm wavelengths. This

instrument was employed at a representative sampling station

during j, situ productivity experiments. The pyranograph

measurements were determined in units of Langleys.hr-1

(ly.hr-1 ). In addition to the pyranograph measurements, a

Protomatic submarine photometer was used to measure incident

and reflected light intensities at each station just below

the water surface and at 1.0 m depth. The photometer

measures light intensities ranging from 300 to 800 nm

wavelength in units of foot-candles (ft-c). These

measurements were made during each monthly survey period and

were used to calculate vertical absorption coefficients at

each sampling station.

Data Analysis

All data analyses were performed using a National

Advanced System (NAS) 5000 computer. Statistical Analysis

System (SAS) (2) and MUSIC interactive programs were used

for all computations, nonparametric analysis of variance,

and Student-Newman-Keuls multiple range analysis. The

32

statistical tables in Zar (6) were consulted in tests for

significance.


1. Bulleid, N. C. 1978. An improved method for theextraction of adenosine triphosphate from marinesediment and seawater. Limnology andOceanography. 23: 174-178.

2. SAS Institute, Inc. SAS User's Guide: Basics, 1982Edition. Cary, N. C.: SAS Institute Inc., 1982.923 pp.

3. Schindler, P. W., R. V. Schmidt, and R. A. Reid. 1972.Acidification and bubbling as an alternative tofiltration in determining phytoplankton productionby the 1 4 C method. J. Fish. Res. Board Can.29: 1627-1631.

4. Standard Methods for the Examination of Water andWastewater, 14th Ed. APHA-AWWA-WPCF, AmericanPublic Health Association, 1975.

5. Steeman-Nielson, E. 1952. The use of radioactivecarbon (14C) for measuring organic production inthe sea. J. Cons. Internat. Mer. 18: 117-140.

6. Zar, J. E. Biostatistical Analysis, EnglewoodCliffs, N. J., Prentice-Hall Inc., 1974.

33

CHAPTER III

RESULTS AND DISCUSSION

River and Wastewater Flows

The seasonal variation in Red River flows during

preoperational studies is indicated in Table III. In

addition, Table IV shows postoperational river flows and the

mean volume of mill wastewaters discharged per month during

postoperational surveys, along with per cent dilution of

wastewater entering the Red River (v/v).

Preoperational

Red River flows ranged from 99 m3 .sec~ during the

January 1981 survey to 2045 m3.sec~ during the June 1981

survey. In general, flows were higher during the winter

months than during the summer months.

Postoperational

Postoperational Red River flows varied seasonally from

159 m3.sec~I in October 19.82 to 1842 m3.sec~ in December

1982. Postoperational flows are summarized in Table IV

where mean monthly river flows, mean monthly mill wastewater

discharge, and per cent dilution (v/v) of mill wastewaters

to Red River flows are indicated. The mill wastewater

discharge comprised no more than 0.057 per cent of the total

34

35

volume of water in the Red River during any one

postoperational survey.

TABLE III

PREOPERATIONAL RED RIVER MEAN MONTHLY FLOWS (m .sec1 )FOR THE PERIOD NOVEMBER 1980 THROUGH AUGUST 1981

Survey Red River Flows *x

Nov 80 205

Dec 80 368

Jan 81 99

Feb 81 371

Mar 81 201

Apr 81 235

May 81 1107

Jun 81 2045

Jul 81 935

Aug 81 159

* Measured at the Shreveport Louisiana U. S. G. S.gage.

36

TABLE IV

POSTOPERATIONAL RED RIVER MEAN MONTHLY FLOWS AD IP MANSFIELDMILL DISCHARGE LEVELS TO THE RED RIVER (m . sec1)

FOR THE PERIOD OCTOBER 1982 THROUGHAUGUST 1983; PER CENT DILUTION OFMILL EFFLUENT TO RED RIVER FLOW

Survey Red River Mill Per centDate Flows ** Discharge Dilution

X X (v/v)

Oct 82 159 0.09 0.057

*Nov 82 282 0.13 0.046

Dec 82 1842 0.17 0.009

Jan 83 904 0.17 0.018

*Feb 83 1034 0.18 0.017

Mar 83 970 0.19 0.020

Apr 83 420 0.14 0.033

*May 83 953 0.23 0.024

Jun 83 469 0.15 0.032

Jul 83 768 0.08 0.010

*Aug 83 . 0.12

* = Quarterly surveys during which in situ primaryproductivity experiments were conducted.

** = Measured at the Shreveport Louisiana U. S. G. S.gage.

37

IP Mansfield Mill WastewaterCharacteristics

To gain an understanding of the nature of wastewater

being discharged into the Red River during postoperational

studies, a summary of selected water quality parameters for

station WRR is provided in Table V. As previously mentioned

in Chapter II, station WRR was selected at the permit point

to represent overland flow of the wastewaters entering the

Red River. All selected laboratory parameters were

characterized and reported as mean values of three

replicates (except for pH, which was measured in the field).

Phytoplankton Primary Productivity

Preoperational

Lnjjtu primary productivity experiments were conducted

at stations 1RR through 4RR in November 1980, and February,

May, and August, 1981. Data were not obtained at station

3RR during the November 1980 survey or station 4RR during

the February 1981 survey due to sampling difficulties.

Despite this loss of information, the preoperational primary

productivity experiments yielded similar values between

upstream reference and downstream experimental stations.

Table VI shows mean values of three replicate samples of in.

situ phytoplankton determinations made during the

preoperational survey. Also listed in Table VI are results

of Kruskal-Wallis analysis of variance between stations

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TABLE VI

PREOPERATIONALJOED.IVER PHYTOPLANKTON 1 4 C PRODUCTIVITYRATES-(mgC.m hr ) MEAN VALUES OF THREE REPLICATES;

RESULTS OF KRUSKAL-WALLIS ANALYSIS OF VARIANCEBETWEEN STATIONS AND STUDENT-NEWMAN-KEULS

MULTIPLE RANGE TESTS

StationKruskal- S-N-K

Survey 1RR 2RR 3RR 4RR Wallis Grouping of Stations

NOV 80 94 216 a. 79 0.0439 2RR 1RR 4RR

FEB 81 101 187 131 a. NS 2RR 3RR 1RR

MAY 81 13 2 7 21 0.0444 4RR lRR 3RR 2RR

AUG 81 422 413 344 432 NS 4RR 1RR 2RR 3RR

NS = Not Significant (Kruskal-Wallis Test), p<0.05;a = Station not sampled.

and Student-Newman-Keuls (S-N-K) multiple range groupings of

stations. The Kruskal-Wallis test is a nonparametric

technique similar to the parametric analysis of variance

test and the S-N-K procedure is a nonparametric technique

similar to the parametric Duncan's Multiple Range Test for

comparisons. Both of these statistical analyses were chosen

because data did not consistently meet all the assumptions

necessary to apply parametric statistical procedures.

Kruskal-Wallis analysis of variance and S-N-K tests were

also determined for all preoperational and postoperational

water quality parameters.

40

No significant difference (pi0.05) between upstream

reference station and downstream experimental stations was

shown by Kruskal-Wallis tests for February and August, 1981.

(See Table VI.) However, there was a statistically

significant difference (p6:0.05 ) between stations 1RR and 2RR

in November 1980 and May 1981 surveys, with productivity at

2RR greater than at IRR. These differences can be

attributed more to local river fluctuations rather than any

environmental significance since no wastewaters were being

discharged during preoperational studies.

Graphical representations of phytoplankton primary

productivity data for the preoperational surveys are

presented in Figures 3 through 6. Mean values of three

replicates (mgC.m-3.hr~1) are plotted by station for each

survey period. Figures 3, 4, and 6 show comparable values

for the November 1980, February 1981, and August 1981

surveys. Primary productivity values obtained in May 1981

are an order of magnitude less than the other three

preoperational survey periods. An examination of light data

during this survey does not provide a complete explanation

of decreased productivity levels. (See Table XXXII.)

Pyranograph readings during this survey were generally

similar to other preoperational survey periods.

In general, there was a relative increase in

phytoplankton primary productivity from upstream to

downstream locations. Specifically, station 1RR is the

mgCrm-3.hr. Mean

200 +

180 +

160 +

140 +

120 +

100 +

80 +

60 +

40 +

20 +

Station

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3RR

Fig. 3--Phytoplankton primary productivity datafor Red River (mgC'm-3 hr'-) , November 1980. Meanvalues of three replicates.

it

mgC'm-3.hr' Mean

180 +

160 +

140 +

120 +

100 +

80 +

60 +

40 +

20 +

Station

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Fig. 4--Phytoplankton primary productivity data

for Red River (mgC-m-3-hr~ ) . February 1981.

mgCm-3.hr~ Mean

20 +A*A *A

18 +

16 +***A*

14 +

12+**

10 +**

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6+

4 +

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Station 1RR 2RR 3RR 4RR

Fig. 5--Phytoplankton primary productivity data for

Red River (mgCmA3AhrA) . May 1981.

mgC.m-3.hr Mean

400+

350 +**** *** **

250+

******

200+

150 +

100 +

50 +

---------------------------------------------------

S tat ion 1 RR 2 RR 3 RR 4 RR

Fig. 6--PhytoplalktOfl primary productivity datafor Red River (mgC nC-3 hr*1). August 1981.

45

upstream location, and stations 2RR, 3RR and 4RR are the

downstream locations. The reference point used for this

determination was the wastewater discharge site. Table VI

and Figure 6 indicate that phytoplankton productivity rates

peaked in August 1981. Minimum rates were observed in May

1981. (See Table VI and Figure 5.)

Phytoplankton primary productivity rates were highly

variable during preoperational studies. The coefficient of

variation ranged from 8.00 at station 1RR to 25.37 at

station 2RR during the November 1980 quarterly survey. The

February 1981 quarterly survey was also highly variable with

coefficients of variation ranging from 11.76 at station IRR

to 38.85 at station 3RR. Primary productivity rates were

most variable during the May 1981 preoperational survey;

coefficients of variation ranged from 28.27 at station 3RR

to 73.80 at station 1RR. Results from the August 1981

quarterly survey indicate the least amount of sample

variability during preoperational studies; coefficients of

variation ranged from 2.09 at station 3RR to 19.26 at

station IRR.

Postoperational

L nsitu 4e productivity experiments conducted during

November 1982, and February, May, and August, 1983 indicate

results similar to those shown in preoperational studies.

The trend of increased phytoplankton productivity downstream

46

from mill discharge was observed in the postoperational

studies, also. (See Table VII and Figures 7 through 10.)

With the exception of the November 1982 survey, all

postoperational surveys yielded increased productivity rates

downstream from the mill wastewater discharge site. Table

VII shows the results of Kruskal-Wallis analysis of variance

between stations for postoperational surveys. With the

exception of the May 1983 survey, all postoperational

surveys showed between station difference (p 0.05) with

Kruskal-Wallis tests. Student-Newman-Keuls groupings of

stations in Table VII show differences between upstream and

downstream stations during the November 1982 survey, as well

as the February and August 1983 surveys. No statistical

significance was shown in the May 1983 survey, yet the trend

of increased productivity rates downstream from the mill

wastewater discharge site was evident.

Postoperational phytoplankton productivity rates peaked

at stations 3RR and 4RR during the August 1983 quarterly

survey. The lowest postoperational productivity rates were

observed during the February 1983 survey. (See Table VII

and Figure 8.)

Primary productivity rates were highly variable during

postoperational studies, as in previous preoperational

studies. Coefficients of variation during the November

47

TABLE VII

POSTOPERATIONAL3 REDRIVER PHYTOPLANKTON 14 C PRODUCTIVITYRATES-(mgC.m .hr ) MEAN VALUES OF THREE REPLICATES;





NOV 82 202 371 322 407 0.0232 4RR 2RR 3RR IRR

FEB 83 9 8 4 3 0.0245 1RR 2RR 3RR 4RR

MAY 83 326 384 353 398 NS 4RR 2RR 3RR 1RR

AUG 83 282 325 2002 825 0.0378 3RR 4RR 2RR 1RR

NS = Not Significant (Kruskal-Wallis Test), p0.05.

1982 quarterly survey ranged from 4.27 at station 4RR to

11.51 at station 2RR. During the February 1983 survey,

coefficients of variation ranged from 2.60 at station 1RR to

26.91 at station 3RR. Similarly, coefficients of variation

during the May 1983 survey ranged from 1.90 at station 3RR

to 17.82 at station 2RR. The August 1983 survey showed the

greatest amount of sample variability, with coefficients of

variation ranging from 2.41 at station 4RR to 110.78 at

station 3RR.

48

mgC'm- 3 .hr~ Mean

400 +

350 +

300 +

250 +

200 +

150 +

100 +

50 +

Station

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1RR

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Aft A Af

2RR

ft A Af**AAAAA

Aft AAA

* * *

*** *

*A***

AA*A

** **

** ** *

** ** A

*****

**** *

***

Af***

3RR

* ** **AA**AAf* * *

AAAA,

AAAAA

**AAA

AA**A

*AA

**A

AAAWA

AAAAA

**AA

* *

A*f*

AAAAA

* AAAA*A*A*A

***AA

AA*A*

*AAAA

4RR


for Red River (mgC.m3'hr- 1 ) . November 1982.

49

mgC'm3hr- Mean

8+

7+

6+

5 +

4+

3 +

2 +

I +

3 RR 4RR

Fig. 8--Phytoplankton primary productivity data forRed River (mgC-m- 3 -hr-1) . February 1983 .

AAAAA

AAAAA

AAAAA

AAAAA

*****

*****

*****

*****

* ****

its***

*****

*****

* * A*A

** AA

* A*

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AA*AA

AAAA

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AAAAA

AAAAA

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******A* ***

AAAAA

*AAAA

AAAAA

AAAAA

** ** *

* ** **A* A A

*AAA

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*****

*****

* ** A

*A* ***

AAAAA*

A*AAA

AAAAA

AAAAAiAAAAA

*aA*AAAAAAA

iAAala aAA

AaatA AAAA

AAAAAA*aaA

*AAaaAAAAaatA*A *AAaAAAAAA*AA

**t~** *

at ***e t*

-- AAAA --- AAAAA-

2RRStation IRR

mgC.m-3.hr Mean

400 +

350 +

300 #* AN

AN

250 +

AN

200 +

150 "+

100 +*

50 +

Station )

ANN

ANNi

ANN*

NAN *

rA7tNA

NANk

ANN

ANN7t

NAN *

NANkyC

ANN*

*ANA 7

ANN*

NAAk *

NAN C

ANNR


for Red River (mgC'm-3-hr- 1 ). May 1983.

50

* m* *AN

* *NN*A

*N* NA

AN*N *N

AN* A NA

AN*A*A

*NNAN*N

* NNN N

NANNAANANA

ANN*N

ANNN

***AN

AN*NA

NANE

ANNA

**NN

ANN

N *N

A *N

NAN*

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A**N*

NAN

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4 RR

* * *#

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#ANANA

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3RR2RR

51

mgC'm-3'hr~ Mean

2000 +

1800 + ,,AAf****

1600 + Af,

4 ~*****

1400 + Aft

1200 + AA*tf

1000 +frA t19 3

800 + AA

600 +** *ft*tf*

400 +ttff ~ tAtfffff

200 +~ * *~ fftf

Station IRR 2RR 3RR 4RR

Fig. IO--PhytoplanktOfl primary productivity data

for Red River (mgC.m3

hr). August 1983.

52

Chlorophyll a,

Preoperational

A summary of planktonic chlorophyll a, data for the

preoperational surveys is shown in Table VIII. No

TABLE VIII

PREOPERAT3 IONAL RED RIVER PLANKTONIC CHLOROPHYLL ,(mg.chla.m ) MEAN VALUES OF THREE REPLICATES; RESULTS

OF KRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEENSTATIONS AND STUDENT-NEWMAN-KEULS


Station

Kruskal- S-N-K


NOV 80 140 131 142 122 NS 3RR 1RR 2RR 4RR

FEB 81 123 109 117 107 NS 1RR 3RR 2RR 4RR

MAY 81 15 11 11 8 NS 1RR 4RR 2RR 3RR

AUG 81 72 50 39 33 NS 2RR 4RR 3RR 1RR

NS = Not Significant (Kruskal-Wallis Test), p<0.05.

significant difference was shown by Kruskal-Wallis analysis

of variance between stations for any preoperational survey

period. In general, mean chlorophyll a values (mg.chla.m3)

were higher at the upstream reference station than at

downstream experimental stations. It is interesting to note

that May 1981 chlorophyll a values were approximately an

order of magnitude less than other preoperational survey

53

periods. This observation supports the decreased May 1981

planktonic productivity rates indicated in Table VI.

Postoperational

Chlorophyll a concentrations for postoperational

surveys are summarized in Table IX. These mean chlorophyll

a results support parallel primary productivity data

generated during these survey periods. There is a relative

increase in chlorophyll a concentrations downstream from the

mill wastewater outfall. No significant difference (p<0.05)

between stations was shown by Kruskal-Wallis analysis of

variance for three out of four postoperational survey

periods. The November 1982 survey showed a significant

difference between upstream and downstream station

chlorophyll a concentrations. Student-Newman-Keuls

groupings of stations showed no difference between stations

1RR and 2RR, but both stations were significantly different

from both 3RR and 4RR (p<0.05). (See Table IX.)

Turbidity

Preoperational

Preoperational surveys, conducted from November 1980

through August 1981, yielded mean turbidity values as shown

in Table X. Mean values ranged from 13 NTU in August 1981

to 363 NTU in December 1981. Table X also lists

Kruskal-Wallis analysis of variance values for between

54

TABLE IX

POSTOPERAgIONAL RED RIVER PLANKTONIC CHLOROPHYLL s,(mg.chl4.m ) MEAN VALUES OF THREE REPLICATES; RESULTS

OF KRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEENSTATIONS AND STUDENT-NEWMAN-KEULS




NOV 82 57 57 36 28 0.0245 2RR 1RR 3RR 4RR

FEB 83 45 37 30 39 NS 1RR 4RR 2RR 3RR

MAY 83 67 71 69 81 NS 4RR 2RR 3RR 1RR

AUG 83 98 129 67 82 NS 2RR 1RR 4RR 3RR

NS = Not Significant (Kruskal-Wallis Test), p10.05.

station comparisons for each preoperational survey sampled

in this study. In addition, Student-Newman-Keuls multiple

range groupings of stations are shown.

Postoperational

Turbidity measurements taken in postoperational surveys

conducted from October 1982 through August 1983 are

summarized in Table XI. Minimum values were found during

the August 1983 survey, while maximum values were recorded

during the December 1982 survey. In general, turbidity

55

TABLE X

PREOPERATIONAL RED RIVER TURBIDITY (NEPHELOMETRIC TURBIDITYUNITS); MEAN VALUES OF THREE REPLICATES; RESULTS OF

KRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEENSTATIONS AND STUDENT-NEWMAN-KEULS




11-80 26 23 22 21 0.0085 1RR 2RR 3RR 4RR

12-80 363 271 259 242 0.0407 1RR 2RR 3RR 4RR

1-81 18 23 18 19 0.0059 2RR 4RR 3RR 1RR

2-81 40 40 47 39 NS 3RR 2RR 1RR 4RR

3-81 32 41 43 44 0.0360 3RR 4RR 2RR 1RR

4-81 28 26 26 32 NS 4RR 1RR 3RR 2RR

5-81 300 330 300 310 0.0086 2RR 4RR 3RR 1RR

6-81 267 220 257 237 0.0162 1RR 3RR 4RR 2RR

7-81 81 90 70 78 0.0009 2RR 1RR 4RR 3RR

8-81 13 18 17 18 0.0304 4RR 2RR 3RR .IRR


56

TABLE XI

POSTOPERATIONAL RED RIVER TURBIDITY (NEPHELOMETRIC TURBIDITYUNITS) ; MEAN VALUES OF THREE REPLICATES; RESULTS OF



StationKruskal- S-N--K


10-82 38 59 46 52 0.0186 2RR 4RR 3RR 1RR

11-82 93 110 99 88 NS 2RR 3RR 1RR 4RR

12-82 393 505 505 505 NS 3RR 2RR 4RR 1RR

1-83 94 86 89 91 0.010 9 1RR 4RR 3RR 2RR

2-83 81 87 122 104 0.0001 3RR 4RR 2RR 1RR

3-83 144 100 128 128 0.0003 IRR 3RR 4RR 2RR

4-83 71 57 68 70 0.0035 1RR 4RR 3RR 2RR

5-83 78 82 64 88 NS 4RR 2RR 1RR 3RR

6-83 194 146 168 182 0.0347 1RR 4RR 3RR 2RR

7-83 105 112 114 107 NS 3RR 2RR 4RR 1RR

8-83 20 16 19 19 0.0406 IRR 3RR 4RR 2RR

Significant (Kruskal-Wallis Test), p<0.05.NS =_ Not

57

values varied seasonally and decreased in proportion with

river flows. (See Tables III and IV.)

Total Suspended Solids

Preoperational

Total suspended solids (TSS) values for monthly

preoperational surveys are summarized in Table XII. Mean

TSS values ranged from a minimum of 23 mg/L in January 1981

to a maximum of 755 mg/L in May 1981. Table XII presents

the results of Kruskal-Wallis analysis of variance between

station comparisons and S-N-K groupings. Statistical

significance (p0.05) was shown in July and August 1981.

However, judging from the relative difference in values, it

appears that these differences are not biologically

significant. In the case of the July 1981 survey, station

1RR (upstream reference) as shown to be significantly

different from stations 2RR, 4RR and 3RR, in that order.

During August 1981, stations 3RR and 4RR were significantly

different from 2RR, which was different from 1RR. There

appears to be no connection between upstream reference and

downstream experimental site differences.

Postoperational

Postoperational mean TSS summary values and statistical

comparisons are shown in Table XIII. The minimum

concentration of 50 mg/L occurred at station 3RR in August

58

TABLE XII

PREOPERATIONAL RED RIVER TOTAL SUSPENDED SOLIDS (mg/L);MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN

STATIONS AND STUDENT-NEWMAN-KEULSMULTIPLE RANGE TESTS



11-80 93 68 93 99 NS 4RR 3RR 1RR 2RR

12-80 162 195 122 125 NS 2RR 1RR 4RR 3RR

1-81 23 41 26 31 NS .2RR 4RR 3RR 1RR

2-81 114 103 129 120 NS 3RR 4RR 1RR 2RR

3-81 78 95 95 83 NS 2RR 3RR 4RR 1RR

4-81 53 61 63 65 NS 4RR 3RR 2RR 1RR

5-81 755 604 632 625 NS 1 3RR 4RR 2RR

6-81 540 316 373 353 NS 18R 3RR 4RR 2RR

7-81 253 203 117 183 0.0003 1RR 2RR 4RR 3RR

8-81 46 79 117 97 0.0015 3RR 4RR 2RR_ RR


59

TABLE XIII

POSTOPERATIONAL RED RIVER TOTAL SUSPENDED SOLIDS (mg/L);MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN



Survey 1RRI 2RR 3RR 4RR Wallis Grouping of Stations

10-82 62 130 79 93 0.0006 2RR 4RR 3RR 1RR

11-82 213 321 225 275 0.0040 2RR 4RR 3RR 1RR

12-82 761,1307 1196 1391 0.0088 4RR 2RR 3RR 1RR

1-83 145' 161 116 140 NS 2RR 1RR 4RR 3RR

2-83 125 257 313 157 0.0001 3RR 2RR 4RR 1RR

3-83 144 100 128 128 NS 1RR 4RR 3RR 2RR

4-83 711 57 68 70 0.0070 4RR 3RR 1RR 2RR

5-83 731 82 53 96 NS 4RR 2RR 1RR 3RR

6-83 453 527 471 607 NS 4RR 2RR 3RR 1RR7-83 323 335 374 311 NS alR 2RR 1RR 4RR

8-83 771 69 50 85 NS 4RR 1RR 2RR 3RR

NS = Not Significant (Kruskal-Wallis Test) , p<0.05.

60

1983, while the maximum value of 1391 mg/L was observed at

station 4RR in December 1982. Statistically significant

differences were shown between stations in October,

November, and December, 1982 and February and April, 1983.

In all but one of these surveys (April), station 1RR was

shown to have the lowest TSS concentration value.

Ammonia Nitrogen (NH3-N)

Preoperational tests for the presence of NH3-N in

triplicate monthly Red River samples yielded results of 0.0

mg/L for the period November 1980 through August 1981.

Likewise, postoperational analyses resulted in 0.0 mg/L

NH3-N for all survey periods from October 1982 through

August 1983, except December 1982. During this survey, all

replicates from all stations showed NH3-N levels of 0.2

mg/L. Since no difference was shown between any two

stations, no statistical analysis was possible.

Nitrate Nitrogen (NO3 -N)

Preoperational

Preoperational mean nitrate concentrations ranged from

0.0 mg/L in August 1981 to 0.7 mg/L in May 1981. Mean

values for each station are shown in Table XIV, along with

between station S-N-K comparisons. Significant differences

existed only during the February 1981 period. However, the

magnitude of difference was probably not biologically

significant (0.1 mg/L).

61

TABLE XIV

PREOPERATIONAL RED RIVER NITRATE NITROGEN (mg/L) ;MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN



Survey IRR 2RR 3RR 4RR Wallis Grouping of Stations

11-80 0.1 0.1 0.1 0.1 NS 1RR 2RR 3RR 4RR

12-80 0.4 0.4 0.4 0.5 NS 4RR 2RR 3RR 1RR

1-81 0.4 0.4 0.4 0.4 NS .RR 2RR 3RR 4RR

2-81 0.4 0.4 0.4 0.3 0.0008 IRR 2RR 3RR 4RR

3-81 0.5 0.5 0.6 0.5 NS 3RR 4RR 2RR 1RR

4-81 0.2 0.2 0.2 0.2 NS IRR 3RR 2RR 1RR

5-81 0.6 0.6 0.6 0.7 NS 4RR 3RR 1RR 2RR

6-81 0.3 0.2 0.2 0.2 NS 1RR 2RR 3RR 4RR

7-81 0.3 0.3 0.3 0.3 NS 1RR 2RR 3RR 4RR

8-81 0 0 0 0 NS >RR 2RR 3RR 4RR


62

Postoperational

Postoperational mean nitrate values ranged from 0.1

mg/L at all four stations in February 1983 to 2.9 mg/L at

stations 1RR and 3RR in August 1983. Mean values of three

replicates for stations 1RR through 4RR are listed in Table

XV, along with the results of Kruskal-Wallis analysis of

variance and S-N-K groupings. A significant difference was

shown in January, April, and June, 1983. In all cases,

station 1RR was significantly different from station 4RR.

Due to the magnitude of these values, these differences are

probably not biologically significant. Any statistically

significant differences are more a result of data precision

rather than environmental significance. In general, station

1RR had higher NO3 -N values than downstream experimental

stations.

Orthophosphate

Preoperational

Results obtained in preoperational studies are shown in

Table XI. Mean values of ortho PO4 -P of three replicates

per station are listed by survey month. The minimum value

of 0.032 mg/L was observed at station 3RR in April 1981 and

the maximum value of 0.486 mg/L was found at station 4RR in

Decmeber of 1980. Significant differences between stations

was shown by Kruskal-Wallis analysis of variance in

TABLE XV

POSTOPERATIONAL RED RIVER NITRATE NITROGEN (mg/L);MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN




10-82 0.4 0.3 0.3 0.3 NS 1RR 2RR 3RR 4RR

11-82 0.4 0.4 0.4 0.4 NS IRR 2RR 3RR 4RR

12-82 0.2 0.2 0.2 0.2 NS 1RR 2RR 3RR 4RR

1-83 0.3 0.3 0.2 0.2 0.0061 1RR 2RR 3RR 4RR

2-83 0.1 0.1 0.1 0.1 NS 1RR 2RR 3RR 4RR

3-83 0.2 0.1 0.2 0.2 NS IRR 2RR 3RR 4RR

4-83 0.4 0.3 0.3 0.3 0.0086 IRR 3RR 2RR 4RR

5-83 0.4 0.4 0.4 0.4 NS 1RR 2RR 3RR 4RR

6-83 2.3 1.9 2.0 1.7 0.0447 IRR 3RR 2RR 4RR

7-83 2.4 2.4 2.4 2.4 NS 1RR 3RR 2RR 4RR

8-83 2.9 2.8 2.9 3.3 NS 4RR 1RR 3RR 2RR


64

TABLE XVI

PREOPERATIONAL RED RIVER ORTHOPHOSPHATE PHOSPHORUS (rng/L);MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN




11-80 .050 .048 .062 .061 NS 3RR 4RR 1RR 2RR

12-80 .484 .378 .445 .486 0.0082 4RR 1RR 3RR 2RR

1-81 .066 .069 .065 .047 0.0240 2RR 1RR 3RR 4RR

2-81 .110 .0921.088 .082 0.0236 1RR 2RR 3RR 4RR

3-81 .097 .125 .142 .112 NS 3RR 2RR 4RR 1RR

4-81 .044 .0421.0321.039 NS 1RR 2RR 4RR 3RR

5-81 .185 .1631.121 .173 NS 1RR 4RR 2RR 3RR

6-81 .117 .068 .076f.097 0.0215 IRR 4RR 3RR 2RR

7-81 .126 .084 .103 .159 0 .0018 4RR 1RR 3RR 2RR

8-81 .066 .075 .067 .091 NS 4R 2RR 3RR 1RR

NS = Not Significant (Kruskal-WalIis Test), p<0.05.

65

December, January, and February of 1980, and June and July

of 1981. Significant probabilities are given in Table XVI,

along with Student-Newman-Keuls grouping of similar

stations. In general, station 1RR showed relatively higher

O-PO 4-P concentrations in comparison with other stations

during preoperational studies.

Postoperational

Orthophosphate concentrations obtained in

postoperational studies are summarized in Table XVII. The

minimum orthophosphate concentration found in

postoperational studies was 0.030 mg/L at station 4RR during

the May 1983 survey. A maximum value of 0.342 mg/L was

obtained at station 4RR during the December 1982 survey.

This range of orthophosphate concentrations was similar

to earlier preoperational studies. Minimum concentrations

were observed during April and May, while maximum

concentrations were observed in December. This trend was

evident in both preoperational and postoperational studies.

Postoperational studies indicated that during three out of

eleven surveys orthophosphate concentrations were higher at

station 2RR than 1RR. During the other eight

postoperational surveys, orthophosphate concentrations were

higher at station 1RR than at 2RR, indicating that

discharged mill wastewaters were not noticably increasing

O-PO4-P concentrations at downstream sites.

66

Kruskal-Wallis analysis of variance between stations

yielded significant differences in January, February, March,

and August of 1983. Kruskal-Wallis probabilities and

Student-Newman-Keuls groupings of stations are summarized in

Table XVII.

Total Phosphate

Preoperational

Total phosphate concentrations obtained in

preoperational studies showed similar relationships between

orthophosphate concentrations. Minimum total phosphate

levels were observed in April of 1981 (0.124 mg/L at station

2RR), while a maximum value of 1.011 mg/L was determined at

station 1RR in December of 1980. Mean total phosphate

values are summarized in Table XVIII, along with summary

statistics. A significant difference between stations was

observed during the February, June, and July, 1981 surveys.

However, December 1980 and January 1981 surveys did not show

significant difference between stations, as did

orthophosphate levels during these same surveys.

Postoperational

Postoperational total phosphate data are summarized in

Table XIX. Values ranged from 0.103 mg/L in May of 1983 to

0.581 mg/L in December 1982. Kruskal-Wallis analysis of

variance yielded significant difference between stations in

October and November, 1982, and February and August, 1983.

67

TABLE XVII

POSTOPERATIONAL RED RIVER ORTHOPHOSPHATE PHOSPHORUS (mg/L);MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN




10-82 .181 .211 .194 .203 NS 2RR 4RR 3RR IRR

11-82 .040.113.103y.11 7 NS 4RR 2RR 3RR 1RR

12-82 .304 .299 .239 .342 NS 4RR 1RR 2RR 3RR

1-83 .058J. 0 3 7 . 4 4 1 .089 0.0085 3RR 4RR 1RR 2RR

2-83 .058K.0881.083 .060 0.0264 2R 3RR 4RR 1RR

3-83 .129 .0371 .068 .049 0.0005 .RR.3RR 4RR 2RR

4-83 .0851.079 .073 .095 NS 4RR IRR 2RR 3RR

5-83 .035 .033 .031 .030 NS IRR 2RR 3RR 4RR

6-83 .089 .062 .066 .093 NS 4RR 1RR 3RR 2RR

7-83 .195 .170 .121 .120 NS ._R 2RR 3 RR 4RR

8-83 .0421 .0411 .045 .058 0.0464 A4RR 3RR RR,2RR


68

TABLE XVIII

PREOPERATIONAL RED RIVER TOTAL ACID HYDROLYZABLE PHOSPHATEPHOSPHORUS (mg/L) ; MEAN VALUES OF THREE REPLICATES;





11-80 .178 .199 .170 .198 NS 2RR 4RR 1RR 3RR

12-80 1.011 .806 .905 .795 NS 1RR 3RR 2RR 4RR

1-81 .155 .155 .142 .132 NS 2RR 1RR 3RR 4RR

2-81 .156 .157 .169 .176 0.0040 4RR 3RR 2RR 1RR

3-81 .163 .181 .184 .175 NS 3RR 2RR 4RR 1RR4-81 .131 .124 .132 .140 NS 4RR 3RR IRR 2RR

5-81 .350 .326 .252 .214 NS 1RR 2RR 3RR 4RR

6-81 .247 .194 .212 .239 0.0043 1RR 4RR 3RR 2R,

7-811 .209 .153 .201 .217 0.0433 4RR 1RR 3RR 2RR

8-81 .121 .136 .120 .151 NS 4RR 2RR 1RR 3RR


69

These results are comparable to postoperational

orthophosphate data. (See Table XVII.)

Total Organic Carbon

Preoperational

Total organic carbon (TOC) concentrations in the Red

River ranged from 3 mg/L to 18 mg/L during preoperational

studies. Minimum TOC concentrations occurred at upstream

stations (lRR and 2RR) during the January 1981 sampling

period. Maximum TOC concentrations were observed at

stations 1RR and 4RR during the March 1981 survey. The

entire preoperational data set for TOC has been summarized

in Table XX. Mean TOC concentrations (mg/L) are reported by

survey period and station from three replicate samples.

Table XX also shows Kruskal-Wallis analysis of variance

results and S-N-K groupings of stations. Although a

significant difference between stations was found by the

Kruskal-Wallis test for several preoperational surveys, it

appears that the precision of the data makes these

differences occur rather than any real differences of

environmental significance'.

Postoperational

Results from postoperational surveys are summarized in

Table XXI. No data were obtained in June, July, and August,

1983 due to carbon analyzer malfunction. TOC concentrations

ranged from 1 mg/L to 19 mg/L. Minimum TOC concentrations

70

TABLE XIX

POSTOPERATIONAL RED RIVER TOTAL ACID HYDROLYZABLE PHOSPHATEPHOSPHORUS (mg/L); MEAN VALUES OF THREE REPLICATES;





10-82 .217 .270 .235 .249 0.0003 2RR 4RR 3RR 1RR

11-82 .170 .236 .197 .158 0.0437 2RR 3RR 1RR 4RR

12-82 .349 .350 .581 .456 NS 3RR 4RR IRR 2RR

1-83 .180 .169 .153 .183 NS 4RR 1RR 2RR 3RR

2-83 .135 .147 .252 .147 0.0479 3RR 4RR 2RR 1RR

3-83 .264 .163 .251 .251 NS 1RR 3RR 4RR 2RR

4-83 .121 .103 .105 .109 NS 1RR 2RR 4RR 3RR

5-83 .090 .099 .103 .120 NS 4RR 3RR 2RR 1RR

6-83 .291 .299 .289 .329 NS 4RR 2RR 1RR 3RR

7-83 .264 .298 .291 .298 NS 4RR 3RR 2RR 1RR

8-83 .122 .113 .107 .103 0.0087 1RR 2RR 3RR 4RR


71

TABLE XX

PREOPERATIONAL RED RIVER TOTAL ORGANIC CARBON (mg/L);MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN



Survey 1RR 2RRj3RR 4RR Wallis Grouping of Stations

11-80 4 3 7 6 0.0001 3RR 4RR1RR 2RR

12-80 10 9 10 12 0.0306 4RR 1RR 3RR 2RR

1-81 3 3 8 6 0.0001 3RR 4R 1RR 2RR

2-81 11 10 21 10 0.0170 3RR 1RR 4RR 2RR

3-81 18 17 17 18 NS 1RR 4RR 3RR 2RR

4-81 11 10 12 10 0.0244 3RR 1RR 2RR 4RR

5-81 13 13 12 12 NS 1RR 2RR 3RR 4RR

6-81 14 13 11 11 0.0002 1RR 2RR 3RR 4RR

7-81 11 11 12 12 0.0053 4RR 3RR 2RR 1RR

8-81 8 9 9 10 0.0193 4RR 2RR 3RR 1RR

Significant (Kruskal-Wallis Test), p<0.05.NS =o Not

72

occurred at stations 3RR and 4RR during the February 1983

survey period. Maximum TOC concentrations were found at

stations 1RR and 4RR during the November 1982 survey period.

In general, no obvious seasonal pattern was evident in the

TOC data. However, higher TOC concentrations were found

during periods of high flow in the Red River. (See Table

IV.)

Kruskal-Wallis analysis of variance results for post-

operational TOC data indicate significant difference between

stations for several surveys. Here again, these differences

are more a result of the precision of data rather than any

environmental significance.

Dissolved Organic Carbon

Preoperational

Dissolved organic carbon (DOC) data obtained in

preoperational surveys are summarized in Table XXII. DOC

concentrations ranged from 1 mg/L to 15 mg/L. A minimum

mean DOC concentration of 1 mg/L was observed at station 2RR

during the February 1981 survey. However, overall minimum

DOC concentrations were found at all Red River sampling

stations (IRR through 4RR) during the January 1981 survey

period. (See Table XXI.) Maximum DOC concentrations were

observed at stations 3RR and 4RR during the March 1981

survey. These observations of minimum and maximum DOC

concentrations follow a similar pattern with preoperational

73

TABLE XXI

POSTOPERATIONAL RED RIVER TOTAL ORGANIC CARBON (mg/L) ;MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN




10-82 5 4 3 2 0.0202 1RR 2RR 3RR 4RR

11-82 18 16 16 19 0.0267 4RR 1RR 2RR 3RR

12-82 13 13 15 14 NS 3RR 4RR 1RR 2RR

1-83 8 11 8 7 0.0186 2RR JRR 3RR 4RR

2-83 7 5 1 1 0.0081 1RR 2RR 3RR4 R

3-83 6 8 6 6 NS 2RR 4RR 1RR 3RR

4-83 9 5 10 10 NS 4RR 3RR 1RR 2RR

5-83 12 14 11 15 0.0191 4RR 2RR 1RR 3RR

6-83 a

7-83 . .1108-83 . . . , 0

NS = Not Significant (Kruskal-Wallis Test), p<0.05;a = data was not analyzed due to carbon analyzer

malfunction,

74

TABLE XXII

PREOPERATIONAL RED RIVER DISSOLVED ORGANIC CARBON (mg/L);MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN


Station

Kruskal- S-N-KSurvey 1RR 2RR 3RR 4RR Wallis Grouping of Stations

11-80 3 3 3 2 NS 1RR 2RR 3RR 4RR

12-80 9 8 9 9 NS 4RR 3RR 1RR 2RR

1-81 2 2 3 3 NS 4RR 3RR 2RR 1RR

2-81 6 1 9 7 0.0001 3RR 4RR 1RR 2RjR

3-81 8 10 14 15 0.0006 4RR 3RR 2RR 1RR

4-81 6 5 5 5 NS 1RR 2RR 3RR 4RR

5-81 6 6 5 6 NS lRR 2RR 4RR 3RR

6-81 6 7 7 6 0.0080 3RR 2RR 4RR 1RR

7-81 10 10 9 9 NS 1RR 2RR 3RR 4RR

8-81 3 6 4 5 0.0001 2RR 4RR 3RR 1RR

Significant (Kruskal-Wallis Test), p<0.05.NS = Not

75

TOC minimum and maximum concentrations. Any significant

differences between stations can be attributed to the

precision of data rather than biological significance

between stations.

Postoperational

Postoperational DOC data are summarized in Table XXIII.

Mean DOC concentrations ranged from 1 mg/L at stations 3RR

and 4RR in February 1983, and at station 1RR in March 1983,

to 12 mg/L at stations 2RR and 4RR in May 1983. These

minimum/maximum values coincide fairly well with

postoperational TOC data. Again, DOC data were not obtained

for the June through August 1983 surveys due to carbon

analyzer malfunction. Table XXIII lists the results of

Kruskal-Wallis analysis of variance between stations and

S-N-K groupings of stations. The February 1983 analysis

yielded a significant difference between upstream and

downstream stations. Upstream stations showed higher DOC

concentrations than downstream stations. There was no

discernible relationship between other significantly

di-fferent survey periods. Therefore, it appears that these

differences are a result of the precision of data rather

than any environmental detriment.

76

TABLE XXIII

POSTOPERATIONAL RED RIVER DISSOLVED ORGANIC CARBON (mg/L);MEAN VALUES OF THREE REPLICATES; RESULTS OFKRUSKAL-WALLIS ANALYSIS OF VARIANCE BETWEEN




10-82 4 3 3 2 0.0001 1RR 2RR 3RR 4RR

11-82 6 4 2 5 0.0004 IRR 4RR 2RR 3RR

12-82 6 5 7 6 NS 3RR 1RR 4RR 2RR

1-83 6 5 6: 7 NS 4RR 3RR 1RR 2RR

2-83 5 4 1 1 0.0081 1RR 2RR 3RR 4RR

3-83 1 3 4 2 0.0251 3RR 2RR 4RR 1RR

4-83 7 4 8 7 NS 3RR 4RR 1RR 2RR

5-83 9 12 9 12 0.0038 2RR 4R 1RR 3RR

6-83 a

7-831 ..

8-83j. *

NS = Not Significant (Kruskal-Wallis Test), p<0.05;a = data was not analyzed due to carbon analyzer

malfunction.

77

Biochemical Oxygen Demand

Preoperational

Biochemical oxygen demand (BOD5) was analyzed for each

Red River replicate sample in both preoperational and

postoperational aquatic studies. Mean preoperational BOD5

values are presented for, each station in Table XXIV.

Results of Kruskal-Wallis analysis of variance between

stations, as well as S-N-K groupings of stations, appear in

Table XXIV, also. A minimum BOD 5 concentration of 0.3 mg/L

occurred at station 4RR in November 1980. A maximum BODE

concentration of 7.9 mg/L occurred at station 4RR in

February 1981. No apparent seasonal relationship between

BOD5 concentration and any other physical factor was evident

from these analyses. (See Table XXIV.) Kruskal-Wallis

analysis of variance results indicate statistical

significant difference between stations in February, April,

June, and August, 1981. However, no clear distinction

exists between upstream and downstream stations during these

four surveys. Therefore, these differences appear to be a

result of data precision rather than any environmental

difference between stations. (See Table XXIV.)

78

TABLE XXIV

PREOPERATIONAL RED RIVER FIVE-DAY BIOCHEMICAL OXYGEN DEMAND(mg/L); MEAN VALUES OF THREE REPLICATES; RESULTS OF





11-80 1.0 1.8 0.9 0.3

12-80 5.2 4.8 4.6 4.4 NS IRR 2RR 3RR 4RR

1-81 4.4 4.5 4.4 4.1 NS 2RR 3RR 1RR 4RR

2-81 4.0 3.1 3.5 7.9 0.0223 4RR 1RR 3RR 2RR

3-81 2.6 2.3 2.3 2.2 NS lRR 2RR 3RR 4RR

4-81 4.9 4.1 4.0 3.8 0.0156 1RR 2RR 3RR 4RR

5-81 1.8 4.7 1.4 1.6 NS 1RR 2RR 4RR 3RR

6-81 1.3 1.2 2.0 1.2 0.3770 3RR 1RR 4RR 2RR

7-81 2.8 2.8 2.5 3.2 NS 4RR 2RR 1RR 3RR

8-81 4.0 3.1 2.9 3.4 0.0444 1RR 4RR 2RW 3RR

NS = Not Significani (Kruskal-Wallis Test), p<0.05;* 1 Replicate;** 2 Replicates.

79

Postoperational

Postoperational BOD5 data are summarized in Table XXV.

Mean B0D5 concentrations ranged from 0.5 mg/L at station 2RR

in February 1983 to 6.7 mg/L at stations 1RR and 2RR in

August 1983. Also displaiayed in Table XXV are

Kruskal-Wallis analysis of variance between stations results

and S-N-K groupings of stations. These summary statistics

indicate a significant difference (p 0.05) between upstream

and downstream stations in November 1982, February 1983 and

July 1983. In the case of the November 1982 and February

1983 surveys, downstream stations had higher BOD5

concentrations than upstream stations. The relationship was

reversed in the July 1983 survey with upstream stations

having higher BOD5 concentrations than downstream stations.

(See Table XXV.)

True Color

Preoperational

Mean true color values (CU) of three replicates are

given by survey data for each station in Table XXVI. True

color in the Red River ranged from 30 color units (CU) to

160 CU. A minimum value of 30 CU was observed at all

stations in August 1981, while the maximum value of 160 CU

was observed at all stations in December 1980. Results of

80

TABLE XXV

POSTOPERATIONAL RED RIVER FIVE-DAY BIOCHEMICAL OXYGEN(mg/L); MEAN VALUES OF THREE REPLICATES; RESULTS OF





10-82 2.3 2.3 2.2 2.5 NS 4RR 1RR 2RR 3RR

11-82 2.7 2.7 3.2 3.2 0.0057 4RR 3RR 2RR 1RR

12-82 2.5 3.4 3.1 3.0 NS 2RR 3RR 4RR 1RR

1-83 0.8 0.9 1.4 0.9 NS 3RR 4RR 2RR 1RR

2-83 1.0 0.5 1.2 1.2 0.0404 3RR 4RR 1RR 2RR

3-83 2.1 2.5 2.0 2.1 NS 2RR 1RR 4RR 3RR

4-83 1.9 1.7 1.6 1.5 NS 1RR 2RR 3RR 4

5-83 2.6 2.4 2.2 2.3 NS 1RR 2RR 4RR 3RR

6-83 1.8 1.6 1.5 1.5 NS IRR 2RR 4RR 3RR

7-83 1.9 1.8 1.7 1.3 0.001 1RR 2RR 3RR 4RR

8-83 6.7 6.7 6.1 6.2 NS IRR 2RR 3RR 4RR

Significant (Kruskal-wallis Test) , p 5.NS =. Not

81

TABLE XXVI

PREOPERATIONAL RED RIVER TRUE COLOR (COLOR UNITS) BY VISUALMETHOD; MEAN VALUES OF THREE REPLICATES; RESULTS OF





11-80 40 40 40 40 NS 1RR 2RR 3RR 4RR

12-80 160 160 160 160 NS IRR 2RR 3RR 4RR

1-81 47 60 53 53 NS 2RR 4RR 3RR 1RR

2-81 40 40 40 40 NS 1RR 2RR 3RR 4RR

3-81 80 80 80 80 NS 1RR 2RR 3RR 4RR

4-81 40 50 50 50 NS 4RR 2RR 3RR 1RR

5-81 100 100 100 92 NS 2RR 3RR 4R

6-81 83 83 83 92 NS 4RR 2RR 3RR IRR

7-81 75 83 75 75 NS 2RR 1RR 3RR 4RR

8-81 30 30 30 30 NS 1RR 2RR 3RR 4RR


82

Kruskal-Wallis analysis of variance showed no difference

between stations during any preoperational survey period.

(See Table XXVI.)

Postoperational

Table XXVII summarizes mean true color values by survey

period for each station. Values ranged from a minimum of 23

CU at stations 3RR and 4RR in August 1983 to a maximum of

125 CU at all stations in December 1982. Kruskal-Wallis

analysis of variance between stations results show a

significant difference (p<O.05) between upstream (lRR and

2RR) and downstream stations (3RR and 4RR) for the July 1983

survey. However, this difference does not appear to be

environmentally significant, based on true color values from

other survey periods. (See Table XXVII.) No significant

difference between station 1RR and 2RR was observed during

any single postoperational survey, indicating that

discharged mill wastewaters were not affecting true color

downstream from station 1RR.

Apparent Color

Preoperational

Apparent color values in the Red River ranged from 60

color units at stations 1RR in August 1981 to 480 color

units at all stations in December 1980. Table XXVIII

summarizes mean true color values of three replicates by

survey period for each station and shows the results of

83

TABLE XXVII

POSTOPERATIONAL RED RIVER TRUE COLOR (COLOR UNITS) BYVISUAL METHOD; MEAN VALUES OF THREE REPLICATES;





10-82 60 60 60 60 NS 1RR 2RR 3RR 4RR

11-82 48 50 50 50 NS 4RR 2RR 3RR 1RR

12-82 125 125 125 125 NS 1RR 2RR 3RR 4RR

1-83 63 70 70 63 NS 2RR 3RR 1RR 4RR

2-83 90 90 90 90 NS 1RR 2RR 3RR 4RR

3-83 80 70 70 70 NS 1RR 2RR 3RR 4RR

4-83 47 45 52 45 NS 3RR 4RR 1RR 2RR

5-83 48 48 45 48 NS 1RR 2RR 4RR 3RR

6-83 58 53 55 55 NS 1RR 3RR 4RR 2RR

7-83 55 53 50 50 0.0061 IRR 2RR 3RR 4RR

8-83 27 25 23 23 NS 1RR 2RR 3RR 4RR


84

TABLE XXVIII

PREOPERATIONAL RED RIVER APPARENT COLOR (COLOR UNITS)BY VISUAL METHOD; MEAN VALUES OF THREE REPLICATES;





11-80 140 127 120 120 0.0086 IRR 2RR 3RR 4RR

12-80 480 480 480 480 NS 1RR 2RR 3RR 4RR

1-81 100 107 110 107 NS 3RR 4RR 2RR 1RR

2-81 80 90 90 90 NS 4RR 2RR 3RR IRR

3-81 140 140 140 140 NS 1RR 2RR 3RR 4RR

4-81 103 100 107 100 NS 3RR 1RR 2RR 4RR

5-81 275 275 275 275 NS 1RR 2RR 3RR 4RR

6-81 200 200 200 200 NS 1RR 2RR 3RR 4RR

7-81 192 1183 175 175 NS 1RR 2RR 3RR 4RR

8-81 60 70 67 67 NS 2RR 4RR 3RR IRR

NS = Not Significant (Kruskal-Wallis Test), p(0.05.

85


S-N-K groupings of stations. A statistical difference

between upstream and downstream stations was observed in

November, 1980. However, this difference can only be

attributed to variations in natural river conditions, since

mill wastewaters were not being discharged during

preoperational studies.

Postoperational

Apparent color values ranged from 70 color units at

stations 1RR, 3RR, and 4RR in August 1983 to 875 CU at all

stations in December 1982. Mean values of apparent color

are summarized by survey month for each station in Table

XXIX. In addition, Table XXIX shows the results of


S-N-K groupings of stations. There was no significant

difference shown between stations for any postoperational

survey, with the exception of July 1983. During the July

1983 survey, a significant statistical difference was shown

between upstream and downstream stations (p<0.05). However,

based on cummulative analysis-of the entire postoperational

data set, no environmental significance can be attributed to

calculated between station differences. (See Table XXIX.)

86

TABLE XXIX

POSTOPERATIONAL RED RIVER APPARENT COLOR (COLOR UNITS) BYVISUAL METHOD; MEAN VALUES OF THREE REPLICATES;



Station-K u Kruskal- S-N-K


10-82 160 147 153 160 NS 1RR 4RR 3RR 2RR

11-82 225 217 225 225 NS 1RR 3RR 4RR 2RR

12-82 875 875 875 875 NS IRR 2RR 3RR 4RR

1-83 150 150 150 150 NS 1RR 2RR 3RR 4RR

2-83 225 225 225 225 NS 1R 2RR 3RR 4RR

3-83 450 450 450 450 NS

4-83 150 150 150 150 NS .RR 2RR 3RR 4RR

5-83 100 100 100 100 NS 1RR 2RR 3RR 4RR

6-83 250 250 250 250 NS 1RR 2RR 3RR 4RR

7-83 150 183 183 175 0.0073 2RR 3RR 4RR JE

8-83 70 73 70 70 NS 1RR 2RR 3RR 4RR

L4S1 -/YLY1 1 e ,LW= tNot Sign ficant (Kruskcal-wal sTs) 5 .

87

TABLE XXX

PREOPERATIONAL RED RIVER ADENOSINE TRIPHOSHATE(NANOGRAMS/L) ; MEAN VALUES OF THREE REPLICATES

RESULTS OF KRUSKAL-WALLIS ANALYSIS OFVARIANCE BETWEEN STATIONS AND

STUDENT-NEWMAN-KEULSMULTIPLE RANGE TESTS



11-80 1643 1558 1699 1384 0.0096 1RR 3RR 2RR 4RR

12-80 1221 1137 1150 932 0.0316 1RR 3RR 2RR 4RR

1-81 807:3 1028 8947 8867 0.0227 2RR 3RR 4RR 1RR

2-81 1311 1985 1736 2393 NS 4RR 2RR 3RR 1RR

3-81 6427 5220 6607 4780 NS 3RR 1RR 2RR 4RR

4-81 4807 4573 5293 3980 NS 3RR 1RR 2RR 4RR

5-81 3152 3367 3257 3267 NS 4RR 2RR 3RR 1RR

6-81 475 485 470 213 NS IRR 3RR 2RR 4RR

7-81 1236 1425 1276 591 0.0002 2RR 3RR IRR _4]I

8-81 2395 2217 2493 2923 0.0002 R.R. 3RR, 1RR 2RR

NS = Not Significant (Kruskal-WalIis Test), p<0.05.

88

Adenosine Triphosphate (ATP)

Preoperational

Adenosine triphosphate (ATP) concentrations ranged from

213 ng/L at station 4RR in June 1981, to 10287 ng/L at

station 2RR in January 1981. Mean ATP concentrations for

three replicates are provided in Table XXX by survey month

for each station. Also, Kruskal-Wallis analysis of variance

results and S-N-K groupings of stations provide an

indication of between station variances. During the

November and December 1980 and January, July, and August

1981 surveys, statistical difference (p<0.05) was shown

between at least one upstream and downstream sampling

stations. It is, however, difficult to interpret these

differences as environmentally significant. It would seem

that these variations resulted more from data precision than

any environmental factor.

Postoperational

ATP results from postoperational surveys are summarized

in Table XXXI. Mean ATP concentration of three replicates

is given by survey month for each sampling station. ATP

concentrations ringed from 30 ng/L at station 3RR in June

1983 to 28845 ng/L at station 1RR in August 1983. Table

XXXI also lists the results of Kruskal-Wallis analysis of

variance between stations and S-N-K groupings of stations.

89

TABLE XXXI

POSTOPERATIONAL RED RIVER ADENOSINE TRIPHOSPHATE(NANOGRAMS/L); MEAN VALUES OF THREE REPLICATES;



StationKruskal S-N-K

Survey 1RR 2RR 3RR 4RR Wallis Grouping ofStations

10-82* 5850 5500 4770 313

11-82* 6767 6290 5720 312

12-82* 2100 3710 2760 2385 .

1-83 1371 114 135 12 0.0010 IRR 3RR 4RR 2RR

2-83 264 278 281 28 0.0379 1RR 3RR 4RR 2RR

3-83 109 99t 94 10 NS 1RR 4RR 2RR 3RR

4-83 272 246 215 21 NS 1RR 2RR 3RR 4RR

5-83 3173 3595 3610 382 NS 4RR 2RR 3RR lRR

6-83 95 81, 30 101 NS 1RR 2RR 4RR 3RR

7-83 569 565 551 556 NS 2RR 1RR 4RR 3RR

8-83 28845 20660 19258 24136 0.0109 1RR 4RR 2RR 3RR

NS = Not Significant (Kruskal-Wallis Test), p<0.05.** 2 Replicates.

90

It was not possible to calculate analysis of variance or

S-N-K groupings of stations for the October, November, and

December, 1982 survey periods since only two replicates were

analyzed due to difficulties encountered during analyses.

Statistical significant difference (p<0.05) was shown

between stations during January, February and August, 1983.

In all three instances, there was significant difference (p<

0.05) between upstream and downstream stations.

Light

Natural light impinging on the water surface is

composed of many wavelengths. It impinges on the water

surface from many angles and is deflected, as well as

absorbed, by materials that alter the composition of the

downward light path (1). As described previously, the

vertical absorption coefficient (k) quantifies the quenching

of light passing through the water column. The coefficient

of extinction (n) has also been used to describe light

attenuation, and is defined as the logarithm to the base 10

in the formula rather than a natural logarithm (3). Since

absorption accurately refers to the diminuation of light

energy with depth by transformation to heat (2), the

coefficient of absorption was calculated from light

measurements taken during in situ primary productivity

experiments.

91

TABLE XXXII

TOTAL LIGHT ENERGY MEASURED ON THE RED RIVERDURING IN SITU PRIMARY PRODUCTIVITY

EXPERIMENTS (1y'hr~l)

SURVEY PREOPERATIONAL POSTOPERATIONAL

NOV 80

NOV 82 34

FEB 81 18

FEB 83 16

MAY 81 37

MAY 83 55

AUG 81 27

AUG 83 50

92

Preoperational

The total amount of light energy measured on the Red

River during in situ primary productivity experiments, in

units of Langleys per hour, is summarized in Table XXXII.

Both temporal and seasonal variation in available light

energy are shown for each primary productivity sampling

survey. These measurements were obtained with the Belfort

pyranograph. Available light energy ranged from 18 to 37

ly.hr~1 during preoperational in situ primary productivity

experiments.

Results of light measurements taken at the water

surface and at a depth of 1 meter (with the Protomatic

submarine photometer) are listed in Table XXXIII. In

addition, the absorption coefficient (k) was calculated for

each sampling station and is shown in Table XXXIII.

Absorption coefficients varied seasonally and spatially from

2.22 at station 1RR in February 1981 to 16.71 at station IRR

in November 1980. Although the minimum absorption

coefficient (2.22 - station 1RR) was found during the

February 1981 survey, other preoperational k values were

consistently low at all four stations in August, 1981.

In general, absorption coefficients were highest during

winter months and lowest during summer months. (See Table

XXXIII.) Also, there appears to be a proportional

relationship between absorption coefficients and river flows

93

TABLE XXXIII

PREOPERATIONAL RED RIVER LIGHT DATA FOR THE PERIOD NOVEMBER1980 THROUGH AUGUST 1981 DURING IN SITU PRODUCTIVITY

EXPERIMENTS; SURFACE LIGHT (ft-c); LIGHT AT1 METER (ft-c); VERTICAL ABSORPTION

COEFFICIENT (k)

Survey Light at Light at AbsorptionSurface 1 Meter Coefficient

(k)

Nov 80

1RR2RR3RR4RR

Feb 81

1RR2RR3RR4RR

May 81

1RR2RR3RR4RR

Aug 81

1RR2RR3RR4RR

1800600

2400130

450500250

1800250020001700

1500+680370110

0.00010.01010.07010.1001

49.000150.0001

0.2501

0.03010.03010.04010.0101

47.000114.000111.0001

2.6001

16.7111.0210.447.17

2.222.306.91

11.0011.3310.8212.03

3.463.883.523.74

4

94

(i.e. k values were highest when river flows were also

high). (See Table III.)

Postoperational

Total available light energy measured on the Red River

during postoperational inaLtu primary productivity

experiments is also shown in Table XXXII. Light

availability ranged from 16 ly.hr-I during the February 1983

survey to 55 ly.hr~I during the May 1983 survey.

Light measurements taken at the surface and at a depth

of 1 meter (with the Protomatic submarine photometer) are

shown in Table XXXIV, along with vertical absorption

coefficients for each sampling station during

postoperational surveys. Absorption coefficients ranged

from 3.48 at statiin 3RR during the August 1983 survey to

11.72 at station 2RR during the November 1982 survey.

Again, higher absorption coefficients were found during

winter months when river flows were also high than during

summer months when flows were considerably lower. (See

Tables III and IV.)

In order to evaluate.the light attenuation capacity of.

the IP wastewaters in the Red River, a comparison of

absorption coefficients found during preoperational studies

with those found during postoperational studies can be made.

Judging from k values shown in Table XXXIII and Table XXXIV,

95

TABLE XXXIV

POSTOPERATIONAL RED RIVER LIGHT DATA FOR THE PERIODNOVEMBER 1982 THROUGH AUGUST 1983 DURING IN SITUPRODUCTIVITY EXPERIMENTS; SURFACE LIGHT (ft-c);

LIGHT AT 1 METER (ft-c); VERTICAL ABSORPTIONCOEFFICIENT (k)

Survey Light at Light at AbsorptionSurface 1 Meter Coefficient

(k)

240037004000740

1500110010002000

6000410050004800

5600450022002400

3.60010.03010.07010.0201

0.15012.00011.5001

10.0001

3.00012.5001

15.000150.0001

110.000091.000168.000145.0001

6.5011.7210.9510.51

9.216.316.505.30

7.607.405.814.56

3.933.903.483.98

Nov 82

1RR2RR3 RR4RR

Feb 83

1RR2RR3RR4RR

May 83

1RR2RR3RR4RR

Aug 83

1RR2RR3RR4RR

96

there appears to be no appreciable differences between

stations during parallel survey months (i.e. August 1981 to

August 1983), with the exception of the February surveys.

Differences in light availability and river flows between

February 1981 and February 1983 can account for the relative

difference in k values from preoperational to

postoperational surveys. (See Tables XXXII, III, and IV.)

pH

Preoperational

A summary of pH values for Red River sampling stations

1RR through 4RR is provided in Table XXXV. pH values ranged

from 7.0 at stations 2RR, 3RR, and 4RR in July 1981 to 8.2

at stations 2RR and 3RR in April 1981. These values are

within the allowable state of Louisiana standards (6.0 -

8.5) for the Red River in the vicinity of the IP Mill.

(Louisiana Water Quality Standards, 1977, Baton Rouge:

Louisiana Environmental Affairs Commission).

Postoperational

A summary of pH data obtained during postoperational

studies is provided in Table XXXVI. A minimum value of 6.6

was found at stations 1RR, 2RR, and 3RR during the June 1983

survey. The maximum value of 8.3 occurred at station 3RR in

October 1982. These values range within the acceptable

limit (6.0 - 8.5). IP mill wastewaters discharged into the

97

Red River had no noticable effect on the pH of receiving

waters. (See Tables XXXV and XXXVI.)

Correlation of Physical/Chemical ParametersWith Phytoplankton Primary Productivity

To provide an understanding of how selected physical,

chemical, and biological parameters were related to

phytoplankton productivity rates, Spearman's rank

correlation coefficients were calculated for postoperational

studies. Spearman's rank correlation is a non-parametric

test of relationships used to establish whether or not two

variables are correlated. Mean values of each physical,

chemical, and biological parameters were tested against mean

phytoplankton primary productivity rates for each

postoperational survey. Results of Spearman's rank

correlation indicated that Total Organic Carbon (TOC),

Dissolved Organic Carbon (DOC), and Biochemical Oxygen

Demand (3OD5 ) were positively correlated with phytoplankton

productivity rates (rs values of 0.731 (n=12), 0.691 (n=12),

and 0.526 (n=16), respectively). Apparent Color was

negatively correlated with productivity rates (rs value of

-0.547 (n=16)). Other physical, chemical, and biological

parameters analyzed in this study were not correlated with

phytoplankton primary productivity rates.

98

TABLE XXXV

PREOPERATIONAL RED RIVER pH VALUES; SINGLE MEASUREMENTSDETERMINED IN THE FIELD WITH A PORTABLE pH METER

Station

Survey 1RR 2RR 3RR

11-80 7.9 7.9 7.9 7.6

12-80 7.3 7.2 7.2 7.3

1-81 7.9 7.9 7.6 7.9

2-81 7.8 7.9 7.8 7.8

3-81 7.4 7.3 7.3 7.4

4-81 8.0 8.2 8.2 8.0

5-81 7.0 7.1 7.1 7.1

6-81 7.2 7.9 7.0 7.1

7-81 7.1 7.0 7.0 7.0

8-81 8.1 8.1 8.1 8.1

99'

TABLE XXXVI

POSTOPERATIONAL RED RIVER pH VALUES; SINGLE MEASUREMENTSDETERMINED IN THE FIELD WITH A PORTABLE pH METER

Station

Survey 1RR 2RR 3RR 4RR

10-82 7.7 7.9 8.3 8.2

11-82 7.9 7.8 7.8 7.8

12-82 7.5 7.4 7.4 7.5

1-83 7.4 7.2 7.2 7.3

2-83 7.0 7.0 7.2 7.0

3-83 7.4 7.4 7.4 7.5

4-83 7.9 7.9 7.9 7.9

5-83 6.9 6.5 6.9 7.1

6-83 6.6 6.6 6.6 7.2

7-83 7.2 7.2 7.2 6.8

8-83 7.8 7.4 7.8 7.7


1. Cole, G. E. Textbook of Limnology, St. Louis, C. V.Mosby Company, 1979.

2. Westlake, D. F. 1965. Some problems in themeasurement of radiation underwater: A review.Photochem. Photobiol. 4: 849-868.

3. Wetzel, R. G. Limnology, Philadelphia, W. B.Saunders Company, 1975.

100

CHAPTER IV

CONCLUSIONS

This study sought to accomplish two principally-

related objectives. The first objective was to assess the

impact of wastewaters from International Paper Company's

Mansfield paper mill on in situ primary productivity in the

Red River. A second objective was to compare previously

collected preoperational in situ primary productivity values

with postoperational values.

To accomplish the first objective, statistical

comparisons were made between productivity rates at an

upstream reference station above the wastewater discharge

site (IRR) and productivity rates at downstream experimental

stations below the wastewater discharge sites (2RR, 3RR,

4RR). These comparisons were determined during two distinct

phases of study design. Preoperational primary productivity

data were collected on a quarterly basis from November 1980

through August 1981, prior to mill start-up and wastewater

discharges into the Red River. Preoperational data were

used to establish a baseline of river conditions prior to

the discharge of paper mill wastewaters.

International Paper Company began limited operations at

the Mansfield mill in November 1981. Approximately one year

later in October 1982, parallel postoperational primary

101

102

productivity studies were initiated on the Red River and

continued through August 1983.

Results of the preoperational upstream-downstream

comparisons showed no significant differences (p<0.05) for

both February and August 1981 quarterly surveys. However,

both November 1980 and May 1981 quarterly surveys showed

some statistically significant between-station differences

for primary productivity. These differences were attributed

to normal river fluctuations and differences in local light

regimes, since no wastewaters were being discharged during

preoperational studies.

Upstream-downstream in situ primary productivity

comparisons made during postoperational studies indicate

statistically significant between-station differences in

primary productivity for the November 1982 and February and

August 1983 surveys. However, the May 1983 results were not

statistically significant (pl0.05). To interpret these

results, it was necessary to determine whether station 1RR

was statistically significantly different from downstream

experimental stations. This determination indicated that

primary productivity rates at station 1RR were not

statistically significantly greater than downstream stations

during the different surveys. Lower productivity rates

would be expected downstream from the wastewater discharge

site if mill wastes were negatively impacting planktonic

production, due to increased light attenuation in the water

103

column. This relationship was not shown by either primary

productivity values or light measurements obtained

throughout the study.

The second objective of this study was to compare the

postoperational data on Ln situ primary productivity with

preoperational data. Although no statistical analyses were

used to make this comparison, graphical analysis of

productivity values showed no discernible differences

between surveys conducted during similar seasonal periods.

Results of other physical/chemical water quality parameters

analyzed were in agreement with primary productivity

results.

Graphical comparisons of primary productivity rates

between upstream-downstream reference revealed a trend of

increased productivity rates from upstream to downstream

sampling stations. This trend was evident in both

preoperational and postoperational studies. Therefore, it

was not possible to link higher downstream productivity

rates with paper mill discharges. Although seasonal and

spatial differences were shown throughout the entire study

period, no detrimental effects on Red River water quality

due to wastewater discharges were observed. Louisiana water

quality standards also support this conclusion.

Water quality standards for the Red River in the

vicinity of the IP mill near Mansfield dictate the following

limitations:

104

1. DO : 5.0 mg/L

2. pH : 6.0 - 8.5

3. TDS : 780 mg/L

4. cl : 184 mg/L

5. SO4 : 112 mg/L.

pH was the only regulated parameter analyzed in this study.

No violations of this parameter were observed for any

preoperational or postoperational survey.

In summary, the following conclusions were reached

regarding the effects of pulp and paper mill wastewaters on

phytoplankton primary productivity in the Red River.

1. No environmentally significant differences in

upstream-downstream in situ primary productivity

rates were directly attributable to discharged

mill wastewaters.

2. Preoperational-postoperational in situ primary

productivity comparisons showed similar seasonal

trends.

3. A general trend of increasing primary productivity

rates from upstream to downstream locations was

observed in both'preoperational and postopertional

studies.

4. Physical/chemical water quality parameters varied

seasonally, but showed similar preoperational and

postoperational values.

105

5. Total Organic Carbon (TOC), Dissolved Organic

Carbon (DOC), and Biochemical Oxygen Demand (BOD 5 )

were positively correlated with postoperational

phytoplankton primary productivity rates. Apparent

color was negatively correlated with productivity

rates.

BIBLIOGRAPHY

Books

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Mosby Company, 1979.

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Standard Methods for t_h._Examination of Water and

Wastewater, 14th Ed. APHA-AWWA-WPCF, AmericanPublic Health Association, 1975.

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Wastewater, 15th ed., APHA-AWWA-WPCF, AmericanPublic Health Association, 1980.

Vollenweider, R. A., A Manual on Methods for MeasuringPrimary Production in Aquatic Environments, 2nd ed.,London, Blackwell, 1974.

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Journals

Bulleid, N. C., 1978, An improved method for theextraction of adenosine triphosphate from marine

sediment and seawater, Limnology and Oceanography,23: 174-178.

106

107

Cooley, J. M., 1977, Filtering rate performance of

Daphnia Retrocurva in pulp mill effluent.

2. Fiah. Res. Bfd. La.. 34: 863-868.

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Johnson, M. G., 1977, Caloric changes along pulp and

paper mill effluent plumes, 2. Fish. Res. Bd. Can.34: 784-790.

Kelso, J. R. M., 1977, Density, distribution, andmovement of Nipigon Bay fishes in relation to a

pulp and paper mill effluent, 2. Fish. Res. .Bd.Can., 34: 879-885.

Minns, C. K., 1977, Analysis of a pulp and paper millplume, J. Fish Res. Bd. Can., 34: 776.

Moore, J. E. and R. J. Love, 1977, Effect of pulp andpaper mill effluent on the productivity of

periphyton and phytoplankton, J. Fish. Res. Bd.Can. 34: 856.

Rainville, R. P., B. J. Copeland, and W. T. McKean,

1975, Toxicity of Kraft mill wastes to anestuarine phytoplankter, J. Water Poll. Cont.Fed., 47: 487-503.

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108

Strickland, J. D. H, 1960, Measuring the productionof marine phytoplankton. Bull. Fish. Res. Bd.,Canada, 122, 172 pp.

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Unpublished Materials

Engineering Science, Inc., 1979, Environmentalassessment for the IPG-1 containerboard complex,Desoto Parish, Louisiana, Final Report toInternational Paper Company, Mansfield, Louisiana.

Hutchins, F. E., The Toxicity of Pulp and Paper MillEffluent: A Literature Review, EPA-600/3-79-013 Environmental Research Laboratory, Corvallis,OR, 1979.

Preoperational Aquatic Studies at the Mansfield Mills,Volume 2: Baseline Report, May 1982, Institute ofApplied Sciences, North Texas State University,Denton, Texas.

United States Geological Survey, 1978-1981, Waterresources data for Louisiana Vol. I, Central andNorthern Louisiana, Water years 1978, 1979, 1980,and 1981, Water Resources Division, U. S. G. S.,Jonesboro, LA.

Documents

No *606r - UNT Digital Library/67531/metadc503963/m2/1/high_re… · This study encompassed approximately 35 km of the Red River between Shreveport and Natchitoches, Louisiana. The