ALGAL GROWTH PROBLEM I N

W E FORK O F THE

BLACK R I V E R

A REPORT

PREPARED FOR

ASARCO WEST FORK UNIT RT. 1, Box 202C

BUNKER, MO 6 3 6 2 9

ALGAL GROWTH PROBLEM I N

WEST FORK O F THE

BLACK R I V E R

TABLE OF CONTENTS

CONTROL STRATEGIES . . . . . . . . . . . . . . . . . . . . . 1 2

RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

I C P ANALYSES OF SELECTED WATER SAMPLES . . . . . . . . 30

CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . 39

REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . 41

. . . . . . . . . . . . . . . . . . . . . . . ACKNOWLEDGMENTS 44

APPENDIX A NITRATE-NITROGEN CONCENTRATIONS . . . . . . A 1 . A26 APPENDIX B NITRITE-NITROGEN CONCENTRATIONS . . . . . . B 1 . 8 2 6

. APPENDIX C AMMONIA-NITROGEN CONCENTRATIONS . . . . . . C 1 C27 APPENDIX D PHOSPHATE-P CONCENTRATIONS . . . . . . . . D l . D 2 6 APPENDIX E ANCILLARY WATER QUALITY DATA . . . . . . . E l . E5

LIST OF FIGURES

FIGURE 2. 21 SEPTEMBER 1991: CONDUCTIVITY AND TEMPERATURE MEASUREMENTS . . . . . . . . . . . . . . . . . . . .20

L I S T OF TABLES

TABLE 3. I C P ANALYSES OF SURFACE MATERIAL ON BLACKENED ROCKS .21

TABLE 7A. WATER QUALITY REQUIREMENTS FOR SURVIVAL AND GROWTH OF VARIOUS FISH . . . . . . . . . . . . . . . . . . . 27

TABLE 10. STREAM FLOW DATA PROVIDED BY ASARCO (A. MILLER) . .31 TABLE 11. RESULTS OF I C P ANALYSES

SAMPLES COLLECTED 9 AUGUST 1990 . . . . . . . . . . 32

TABLE 12. RESULTS OF I C P ANALYSES SAMPLES COLLECTED 24 AUGUST 1990 . . . . . . . . . 33

TABLE 13. RESULTS OF I C P ANALYSES SAMPLES COLLECTED 27 JUNE 1991 . . . . . . . . . . 34

TABLE 14. RESULTS OF I C P ANALYSES SAMPLES COLLECTED 14 JULY 1991 . . . . . . . . . . 35

TABLE 15. I C P ANALYSES SPECIAL SAMPLES COLLECTED 9 JANUARY 1992 . . . . . . . . . . . . . 37

ALGAL GROWTH PROBLEM WEST FORK O F T H E BLACK RIVER

BACKGROUND: Construction of the ASARCO West Fork Mine-Mill complex began in 1980. Work was

interrupted from 1982 to 1984. By late 1985 or early 1986 the unit was reported to be operating at about 40% capacity. Production reached 100% capacity in 1988, with a work force of approximately 100 to 150 employees. Early reports of industrial activities indicated that the mine was producing approximately 3800 tons of ore per day, with an average lead content of 7%, 1.9% zinc, and 1/3 oz of silver per ton of ore. Annual production was reported a t 66,000 tons of Pb, 15,000 tons of Zn, and 350,000 oz. Ag, all a s concentrates produced by the mill (Missouri Department of Natural Resources, 1992).

Ore is mined approximately 1000 feet underground from aquiferous dolomitic host rock strata. Much of the water pumped from underground is used within the mill for its hydrometallurgical separations. All mill tailings and process water a r e delivered to a 3200 acre-ft main settling pond which is designed for 100% recycle of mill water. This main settling pond is held in an adjacent valley by a large primary dam and clay liner. A secondary dam and pond a t the base of the main dam traps seepage from the main dam and collected seepage is pumped back into the main tailings pond. Excess mine water is pumped to the surface and delivered into a baffled lagoon. Permits required by the Missouri Department of Natural Resources allow the release of up to 6.48 million gallons per day of treated mine water to be discharged through baffled decant lines. Actual monitored discharges amount to approximately 1000 to 1200 gpm, which translate into approximately 1.44 to 1.73 mgd. Discharged water flows through a short discharge channel and weir into the West Fork of the Black River.

T H E PROBLEM

The ASARCO West Fork mine-mill complex has been in operation only a relatively short time, since the late 1980's. From all available data, it would appear that the industrial operations a re conducted in compliance with regulations established by state and federal regulatory agencies. Some local landowners have complained, however, that river conditions in the West Fork of the Black River have changed noticeably since industrial operations began. Immediately below the industrial discharge, water sometimes appearsLurbid or cloudy, and the rocks on the bottom o f a e river are sometimes discolored with rusty, dark brown, or i-urther downstream and extending into the

-

-el' some 200 yards downstream, the rocks sometimes become covered with slimy dark-brown material, quite dissimilar to conditions upstream of the mine. In places, the brown mat often covers the entire river bottom, with large chunks of organic matter sometimes dislodging and floating downstream. Some complain that favorite old swimming holes or fishing holes like the Grand Daddy Hole a re frequently fouled by the 'discolored organic mats and trapped debris.

In response t o questions raised by local landowners, and in cooperation with the Missouri Department of Natural Resources and' the University of Missouri-Rolla, a study was initiated in June, 1990 to investigate the reported problem in the West Fork of the Black River. Specific objectives of the study were:

1. To determine the nature and major constituents of the dense biological mats which develop to nuisance proportions during the summer months along portions of the West Fork of the Black River, especially downstream from the industrial discharge of the ASARCO West Fork minewater pond. 2. To determine possible causes or contributing factors for the seasonal biological blooms.

3. To determine the nature and cause of noticeable discoloration of rocks and vegetation in the vicinity of the ASARCO minewater pond discharge. To determine possible reasons for abrupt changes in the composition and appearance of the benthic (river bottom) community adjacent to and downstream from the ASARCO West Fork industrial discharge. 4. T o determine possible or relative contributions of the ASARCO West Fork industrial discharges to the nuisance biological mat problem. 5. To make recommendations for methods to improve the problem.

Specifically, the initial research plan identified eleven primary sampling sites along the West Fork of the Black River and its tributaries, Bills Creek and Mill Creek, upstream and downstream from the ASARCO minewater pond discharge. These sites a re indicated in the map shown in Figure 1, and may be further described as shown in Table 1.

Table 1 SAMPLING SITES

The initial study period extended from June, 1990 to November, 1991. Weekly samples were taken from each of the primary sites during the summer months of 1990 and 1991, interspersed with monthly samples throughout the rest of the study period. Actual dates of sample collection are shown in Table 2.

SITE #

1

2

3

4

5

6

7

8

9

10

11

DESCRIPTION

West Fork Northwest Low Water Crossing

Bills Creek Low Water Crossing on County Road

Bills Creek, Upstream near Doe Run Tailings Pile

Brushy Creek Mine Discharge (Doe Run)

West Fork approximately !h mile downstream from Bills Creek

West Fork a t Old Highway KK crossing

West Fork Mine Pond Discharge Pipes

Minewater pond influent pipe

West Fork Grand Daddy Hole

West Fork 1% miles Downstream from Mine

Mill Branch a t confluence with West Fork of Black River

Table 2 SAMPLING DATES

.

TV RECORDINGS & ALGAE SAMPLES

715 TV TAPE & ALGAE

811 TV TAPE & ALGAE

8/19 TV TAPE & ALGAE

8/24 ALGAE

8/26 TV TAPE & ALGAE

913 TV TAPE & ALGAE

1015 ALGAE 10114 TV & ALGAE

1116 TV TAPE & ALGAE

1212 ALGAE

2/10 ALGAE

517 ALGAE

6/12 TV TAPE & ALGAE

6/28 ALGAE

7/14 ALGAE

7/19 TV TAPE & ALGAE

WEEK #

1

2

3

4

5

6

7

8 L

9

10

11

12

13

14

15

20

24

29

33

37

41

46

50

51

52

53

55

56

DATE

28 June 1990

5 July 1990

13 July 1990

19 July 1990

26 July 1990

1 August 1990

9 August 1990

16 August 1990

24 August 1990

31 August 1990

7 September 1990

14 September 1990

21 September 1990

28 September 1990

5 October 1990

6 November 1990

3 December 1990

11 January 1991

6 February 1991

6 March 1991

5 April 1991

9 May 1991

6 June 1991

12 June 1991

20 June 1991

27 June 1991

11 July 1991

18 July 1991

912 TV TAPE & ALGAE

912 TV TAPE & ALGAE

9/21 TV TAPE & ALGAE

57

58

60

61

62

65

74

25 July 1991

1 August 1991

15 August 1991

22 August 1991

29 August 1991

21 September 1991

19 November 1991

In addition to the eleven regular sampling sites, comparison samples were occasionally taken f rom several regional springs and streams, including Meramec Spring, Lane Spring, Montauk Spring, Welch Spring, Martin Spring (Rolla), Love Creek (Rolla), Little Beaver Creek (Rolla), and an unidentified spring in the West Fork of the Black River near the ASARCO mine pond discharge. Love Creek and Little Beaver Creek in the vicinity of Rolla receive sewage effluent and display frequent algal blooms. Regional springs are known to support sustained growth of aquatic plants, including periodic algal blooms, in the vicinity of spring emergence.

METHODS:

Water samples were routinely collected in clean plastic bottles and transported to the UMR laboratory. Analyses were normally conducted the same day for NITRATE-N, NITRITE-N, AMMONIA-N, AND PHOSPHATE-P, using procedures, reagents, and standards obtained from Hach Chemicals, Loveland, Colorado. All analytical procedures were approved by the USEPA for water and wastewater analysis. Results a re reported in terms of ppm or mg/L.

During the latter part of the study, occasional measurements were also performed to determine pH, conductivity (psiemenslcm), total dissolved solids (mg/L), Alkalinity (mg/L as CaCO,), and total hardness (mg/L as CaCO,).

On indicated dates, samples of benthic mats or filamentous algae were collected in clean plastic tubes and returned to the UMR laboratory for microscopic analysis. Major constituents were identified by visual inspection and use of appropriate keys (Prescott, 1978; American Public Health Association, 1971; Needham and Needham, 1978).

As indicated, television tape recordings were occasionally made of field conditions and typical microscopic fields during laboratory analysis to document general conditions, extent of biological growth, and specific major constituents of benthic biota.

On several occasions, aliquots of water samples collected from primary sampling sites or other selected sites were acidified with reagent grade HNO, (final concentration = 1%) and taken for elemental analysis by induction coupled argon plasma (ICP) spectrographic techniques. ICP analyses were performed by the Environmental Trace Substances Research Center, Columbia, Missouri.

REVIEW O F LITERATURE PERTAINING T O ALGAL BLOOMS

Phycology, the study of algae, has long been an integral part of scientific investigation. The scientific literature contains large numbers of papers dealing with the properties, characteristics, and life cycles of many different species of algae. Fuller and Tippo (1954) estimated that there a r e some 1,500 genera and 17,400 species of algae. The biology of algae is an important aspect of any study of the aquatic environment. Increasing awareness of environmental problems associated with lakes, reservoirs, rivers and streams of industrialized nations has focused attention on algae, as they often serve a s indicators of water quality. Excessive algal growth is readily recognized as evidence of eutrophication -- the accumulation of plant nutrients in the aquatic environment. Recent summarizing texts and monographs, readily available in practically any library, offer a great deal of information about algae. (See Jackson, 1964; Tilden, 1968; Fogg, e t al., 1973; and Sze, 1986)

The growth of nuisance quantities of algae in rivers, streams, lakes, rivers, and other water impoundments is a widespread phenomenon. Algae grow wherever there is water and the necessary dissolved inorganic nutrients required for growth. Excessive growth in public water supplies has resulted in many serious problems: discoloration of the water, the production of objectionable odors and tastes, clogging of filters, choking and blocking water distribution and irrigation systems, creating aesthetic problems with the development of unsightly mats, and occasional episodes of toxicity to fish and domestic animals due to algal metabolites or anoxia created by decomposing algae.

Algae a r e found in every non-toxic aquatic habitat. They constitute a primary source of food fo r fish and other aquatic organisms, and a r e thus an important part of natural food chains. Without

algae, many of the other normal aquatic organisms could not exist. There are many kinds, shapes, and colors of algae. Algae may be free-floating or free-swimming or attached to rocks and other vegetation. They may be single-celled, filamentous, o r colonial, and may give a "pea soup" appearance to an entire lake or pond, or form dense fibrous, slimy, or bubbly gelatinous mats which cling to submerged rocks and higher plants. In highly enriched streams, green algal filaments create streamers that may exceed 50 feet in length, providing an excellent environment for blackfly larvae, midge larvae and other nuisance animals. Massive floating algal scum sometimes obstructs navigation, disrupts recreational areas, removes dissolved oxygen from the water when decomposing, killing other desirable aquatic life a s a result, fouls fish harvesting equipment, o r when washed upon the shore by wind and wave action creates unbearable odors and unsightly appearance. Many algae a re various shades of green, others a re blue-green, brown, tan, yellow, orange, or red. They are photosynthetic and capable of fixing carbon dioxide and other inorganic substances into the complex carbohydrates, lipids, proteins, nucleic acids, etc. that form living protoplasm. A s they grow and reproduce, they become food for many small and large grazing animals, and a r e indispensable as a food source for productive streams, rivers, and lakes. Some are capable of existing heterotrophically, when the occasion demands, utilizing organic food substances for growth rather than depending on photosynthesis. They produce food and oxygen when photosynthesizing. At night, o r when living heterotrophically, they consume oxygen and stored organic foods, and release carbon dioxide. Like all living things, they excrete and secrete a variety of metabolic products, by-products, and wastes. The types and abundance of secreted products may have profound effects upon other algae, higher plants, and animals.

When algae grow rapidly in an aquatic environment, they are said to "bloom." Blooms may result in dense algal communities where one, or two or perhaps a few species a re dominant, excluding all other types, and encouraging the development of certain restricted types of consumer organisms. The dominant forms may or may not be aesthetically pleasing to humans. Other communities may form where there are many co-dominant species that co-exist in a very complex community. The factors that determine or allow community development are poorly understood. It is difficult to predict just what type of community will be established from one site to another or from one season to another. In temperate climates, however, a very general pattern of algal community development has been observed. Diatoms (commonly forming golden, tan, or brownish gelatinous or slimy mats or evenly suspended cells) dominate algal communities during the winter and early spring. These a re commonly replaced or joined by green filamentous algae in late spring and early summer. Blue-green algae, together with associated diatoms, often dominate during the late summer months when temperatures a re high. Algal communities commonly change in abundance and constituents with time and changing nutrient and climatic conditions. Many poorly defined and poorly understood biological factors also exert an influence on the development and maintenance of algal communities. A s a dominant algal species grows, it often produces wastes or other "metabolites" and sometimes algal- specific viruses and pathogens (disease-causing microorganisms) sweep through the community, which interfere with further growth and development of that species and perhaps others. Non-affected species may suddenly reproduce rapidly, taking advantage of available nutrients, until some new factor becomes limiting. Conditions a re significantly different in lakes and rivers, and community patterns and growth rates may, therefore, be radically different. Thus, in any habitat and its developing community, there are many integrated life cycles, blooms followed by periods of decline and death of some species and secondary blooms of other species, resulting in complex patterns of succession. Algae a re producers. They eventually a re consumed by grazing protozoans or larger animals. Though bacteria and fungi (decomposers) do not normally attack healthy algae, they may participate in decomposition of damaged or dead algae. Rapid decomposition may be accompanied by lowered oxygen concentrations and foul odors.

In the summary document issued in 1969 by the U.S. Department of Interior, Federal Water Pollution Control Administration entitled "The Practice of Water Pollution Biology" (Mackenthun, 1969), the process of eutrophication and algal growth a r e discussed extensively. The author points out that eutrophication is a term meaning enrichment of waters by nutrients through either man-created or natural means. Present knowledge indicates that the fertilizing elements most responsible for lake

eutrophication are phosphorus and nitrogen. Iron and certain "trace" elements a re also important. When algal cells die, oxygen is used in decomposition and fish kills have resulted. Rapid decomposition of dense algal scums, with associated organisms and debris, gives rise to odors and hydrogen sulfide gas that creates strong citizen disapproval. Nitrogen and phosphorus are necessary components of an environment in which excessive aquatic growths arise. Algal growth is influenced by many varied factors: vitamins, trace metals, hormones, auxins, extracellular metabolites, autointoxicants, viruses and predation and grazing by aquatic animals. Several vitamins in small quantities a re requisite t o growth in certain species of algae. In a freshwater environment, algal requirements a re met by vitamins supplied in soil runoff, lake and stream bed sediments, solutes in the water, and metabolites produced by actinomycetes, fungi, bacteria, and several algae. Evidence indicates that: (1) High phosphorus concentations are associated with accelerated eutrophication of waters, when other growth promoting factors a re present; (2) aquatic plant problems develop in reservoirs or other standing waters at phosphorus values lower than those critical in flowing streams; (3) reservoirs and other standing waters collect phosphates from influent streams and store a portion of these within consolidated sediments; and (4) phosphorus concentrations critical to noxious plant growths vary, and they produce such growths in one geographical area, but not in another. The following potential contributors of phosphorus to the aquatic environment have been identified: Major Contributors:

Sewage and Sewage Effluents: 3 Ibs. per capita per year. Some industries, e.g., potato processing: 1.7 lb. per ton processed. Phosphate rock from 23 states (Mackenthun and Ingram, 1967). Cultivated agricultural drainage: 0.35-0.39 lb. per acre drained per year

(Engelbrecht and Morgan, 1961) (Sawyer, 1947) (Weibel, 1965). Surface irrigation returns, Yakima River Basin: 0.9-3.9 lbs. per acre per year

(Sylvester, 1961). Benthic Sediment Releases.

Minor Contributors: Domestic duck: 0.9 lb. per year (Sanderson, 1953). Sawdust: 0.9 lb. per ton (Donahue, 1961). Rainwater, a s air pollutants a re washed out of the atmosphere. Groundwater, Wis.: 1 lb. per 9 million gals. (Juday and Birge, 1931). Wild duck: 0.45 lb. per year (Paloumpis and Starrett, 1960). Tree leaves: 1.8-3.3 lb. per acre of trees per year (Chandler, 1943). Dead Organisms, animal excretions.

Keup (1968) in flowing water studies found that phosphorus is temporarily stored in bottom sediments or transported a s a portion of the stream's bed-load after its removal from the flowing water. Long-term storage is affected when the phosphorus is pooled in deltas or deposited on flood plains. Mobility and bioavailability of phosphorus in sediments of deeper waters vary, generally inversely related to depth of position within the bottom sediments, pH and water hardness. Once nutrients a re combined within the ecosystem of the receiving waters, their removal is tedious and expensive. In a lake, reservoir, or pond, phosphorus is removed naturally only by outflow, by insects that hatch and fly out of the drainage basin, by harvesting a crop, such a s fish, and by combination with consolidated bottom sediments. Even should adequate harvesting methods be available, the expected standing crop of algae per acre often exceeds 2 tons and contains only about 1.5 lbs of phosphorus. Similarly, submerged aquatic plants could approach at least 7 tons/acre (wet weight) and contain 3.2 lbs/acre of phosphorus. Considering a phosphorus content of 0.7 percent, 1 pound of phosphorus could be distributed among 1,450 pounds of algae on a wet weight basis. The harvestable fish population (500 lbs) from 3 acres of water wouuld contain only 1 lb of phosphorus.

Chu (1943) found that optimum growth of all organisms studied in laboratory culture can be obtained in nitrate-nitrogen concentrations from 0.9 to 3.5 mg/l and phosphorus concentrations from

0.09 to 1.8 mg/l. Limiting effects on all organisms were found in nitrogen concentrations <0.1 mg/l and phosphorus concentrations ~ 0 . 0 0 9 mg/l. Sylvester (1961) found that nuisance algal blooms were observed in Seattle's Green Lake (a very soft water lake) when nitrate-nitrogen was >0.200 mg/l and soluble phosphorus was >0.010 mg/l. Sawyer (1947) found that 0.30 mg/l inorganic nitrogen and 0.01 mg/l soluble phosphorus a t the start of the active growing season could produce nuisance algal blooms. Gerloff and Skoog (1957) and Lund (1965) suggest that nitrogen appears to be the more critical factor limiting algal production in many natural waters. Because of their innate ability to utilize atmospheric nitrogen, many blue-green algae and diatoms are especially effective in competing under conditions of limiting nutrients (Fogg, e t al. 1973).

Muller (1953) concluded that excessive growths of plants and algae in polluted waters can be avoided if the concentration of nitrate nitrogen is kept below about 0.3 mg/l and the concentration of total nitrogen is not allowed t o rise much above 0.6 mg/l. A considered judgement suggests that to prevent biological nuisances, total phosphorus should not exceed 0.100 mg/l a t any point ,within the flowing stream, nor should 0.050 mg/l be exceeded where waters enter a lake, reservoir, o r other standing water body. Those waters now containing less phosphorus should not be degraded (Mackenthun, 1968, 1969).

The following is taken from Mackenthun (1969), beginning on page 41:

" I t i s generally conceded that abundan t ma jor nu t r i en t s i n t h e f o r m of available n i t rogen and p h o s p h o r u s are an important and a necessary c o m p o n e n t o f an e n v i r o n m e n t i n which excess ive aquat ic growths arise. Algae , however , are i n f l u e n c e d b y m a n y and varied fac tor s . V i t a m i n s , trace me ta l s , h o r m o n e s and aux ins , extracel lular me tabo l i t e s , au to in tox i can t s , v i ruses , and predat ion and grazing b y aquat ic an ima l s are fac tors that s t imu la te or r educea lga lgrowths . S o m e o f t h e s e may b e of equal impor tance t o t h e ma jor nu t r i en t s i n i n f l u e n c i n g nu i sance algal b l o o m produc t ion .

Harder, i n 1917, i s credi ted with t h e f i r s t connec t ing growth inh ib i t i ng subs tances with algae. A s early as 1931, au to inh ib i t i ng subs tances were recognized ( A k e h u r s t , 1931) . T h e s e papersgave r i se t o a c o m m o n bel ie f that a plant can create i t s s e l f - d e s t r u c t i o n through t h e produc t ion of growth inh ib i t i ng subs tances that i t cannot to lerate b u t which may , i n t h r n , s t imu la te o ther growths . Natural waters con ta in t h e s e ac t ive agents that are secreted a n d excreted by f r e sh water algae. T h e tox i c i t y of t h e s e agents t o o ther algae and bacteria a n d t o f i s h varies cons tan t l y and i s n o t well unders tood i n t h e natural aqua t i c e n v i r o n m e n t . I t has been pos tu la ted that algae secre te n o t just o n e subs tance bu t several , s o m e an t ib io t i c , o thers s t imulat ing . T h e a m o u n t secre ted and t h e n e t resul t o f t h e secre t ions would b e de t e rmined b y t h e prevalence of o n e group of subs tances over the o ther . T h u s , s equences o f algal b l o o m s may b e expected t o occur under c o n d i t i o n s of a nu t r i en t supp ly far i n exces s of critical values.

Fitzgerald ( 1 9 6 4 ) d i scussed t h e sequences of algal b l o o m s that occur under c o n d i t i o n s o f nu t r i en t supp ly i n sewage s tabi l i za t ion p o n d s far i n excess o f t h o s e f o u n d i n natural lakes . H e a l s o rev iews s o m e of t h e fac tors o ther than nu t r i t i on that m igh t i n f l u e n c e t h e algal popu la t ion . T h e s e fac tors i n c l u d e grazing and t h e produc t ion of i nh ib i t i ng extracel lular products . I t i s poin ted o u t that there i s ev idence that an inverse re la t ionsh ip f r e q u e n t l y ex is t s be tween t h e d e n s i t y of phy top lank ton and zoop lank ton . T h i s m igh t b e t h e resul t of over-grazing i n s p e c i f i c areas and a lack of grazing i n ad jo in ing areas or i t may b e d u e t o an "exc lus ion" e f f e c t o n z o o p l a n k t o n produced by ex trace l lu larplant me tabo l i t e s . G ibor ( 1 9 5 7 ) has s h o w n ev idence that algae

can at t i m e s pass t h rough t h e zoop lank ton w i thou t be ing a f f e c t e d b y d iges t ive processes .

I n s i t ua t ions where t h e algae are s o abundan t that t he i r con t ro l m a y be required b y chemica l means , i t appears that an ima l predat ion or a t tacks b y micro -organ i sms are no t enough t o cause a s h i f t i n t h e d o m i n a n t spec ies . O n c e t h e d o m i n a n t spec ies i s e l im ina ted , however , o ther spec i e s increase i n n u m b e r s and b e c o m e d o m i n a n t . Factors t h o u g h t t o con t r ibu te t o spec i e s d o m i n a n c e i n c l u d e secreted or excreted inh ib i t i ng extracel lular p roduc t s ( R i c e , 1954) .

Le f evre ( 1 9 6 4 ) stated that when an algal spec i e s d e v e l o p s ex t ens i ve l y i n s tanding waters caus ing waterblooms, i t eventual ly b e c o m e s in tox icated by i t s own accumula ted excre t ion pro'ducts and d i e s . W h e n t h e water i s renewed s lowly , t h i s p h e n o m e n o n d o e s n o t occur because t h e extracel lular p roduc t s are cons tan t l y r e m o v e d . A l s o , when o n e spec ie s o f algae predomina te s i n s tanding water, o ther spec i e s appear o n l y sporadically and t h e n u m b e r of bacterial spec i e s decreases . L e f e v r e e t a l . ( 1 9 5 2 ) suggested that t h i s p h e n o m e n o n i s d u e t o antagonis t ic subs tances produced by the .predominan t spec ies . I n m a n ' s ques t t o r educe ma jor nu t r i en t s enr iching waters, s u c h as n i t rogen and p h o s p h o r u s , and thereby res tore s u c h waters t o a greater water u s e potent ia l w i thou t a t t endan t algal pes ts , o ther algal popu la t ion i n f l u e n c i n g fac tors wil l have a ro l e i n t h e u l t ima te success of t h e res torat ion e f f o r t s . T h i s r o l e i s present ly ne i ther clearly d e f i n e d n o r u n d e r s t o o d . I t d o e s s e e m clear that t h e cons tan t progression o f t h e geologic c lock canno t b e subs tant ia l ly a l tered . Desp i t e m a n ' s m o s t a rden t d reams , l akes n o w f e r t i l e and abundan t l y p roduc t i ve o f algae wil l never again at tain the i r crystal-clear, pr is t ine appearance s o well impr in t ed i n t h e m i n d s of l o n g - t i m e local r e s iden t s . T h e o l d - s w i m m i n - h o l e l ingers o n i n local f o l k l o r e . Recen t l y d e f i l e d waters can b e i m p r o v e d subs tant ia l ly , however , b y reducing or r emov ing t h e varying causes of algal p roduc t i v i t y . By placing a l l k n o w n algal popu la t ion i n f l u e n c i n g fac tors i n t he i r proper perspect ive and b y i n t e n s i f y i n g inves t igat ive e f f o r t s d irec ted towards t h e in t e r re la t ionsh ips o f fac tors m o s t l i ke l y t o e f f e c t popu la t ion c o n t r o l s , knowledge and nu i sance reduc ing e f f o r t s wil l b e enhanced . Lakes , reservoirs , p o n d s , f l owing s t reams, es tuar ies , and bays will b e i m p r o v e d , and t h e us ing pub l i c wil l be b e n e f i t e d .

Eys ter ( 1 9 6 4 ) d i v ided t h e e l e m e n t s required by green p lants i n t o macronu t r i en t s and micronu t r i en t s . Macronutr ien ts i n c l u d e carbon, hydrogen, oxygen, n i t rogen, p h o s p h o r u s , s u l f u r , po tas s ium, m a g n e s i u m , ca lc ium ( e x c e p t f o r algae where i t i s a m i c r o n u t r i e n t ) , and s o d i u m . Micronu t r i en t s i n c l u d e i ron , manganese , copper , z inc , m o l y b d e n u m , vanad ium, b o r o n , ch lor ine , cobal t , and s i l i con .

Manganese i s o n e of t h e k e y e l e m e n t s i n pho tosyn thes i s and manganese- d e f i c i e n t c e l l s have a reduced l eve l o f p h o t o s y n t h e s i s and a reduc t ion i n ch lorophy l l . I r o n i s associa ted with n i t rogen m e t a b o l i s m . A r n o n ( 1 9 5 8 ) c o n f i r m e d that ch lor ide Is a c o e n z y m e o f p h o t o s y n t h e s i s spec i f i ca l l y concerned with oxygen e v o l u t i o n . V a n a d i u m and z inc appear t o b e i n v o l v e d i n pho tosyn thes i s . C a l c i u m and boron are invo lved i n n i t rogen f i xa t ion .

M o l y b d e n u m i s necessary f o r n i t ra te u t i l i za t i on and n i t rogen f i xa t i on C o b a l t i s a s soc ia t ed wi th t h e nutr i t ional f u n c t i o n s of v i tamin B - 12."

Certain algae, particularly some of the blue-green species and the dinoflagellates responsible for Red Tides, produce significant quantities of toxins when they grow in bloom proportions. These poisonous substances have been known to have dramatic effects on the aquatic community as well as terrestrial animals who drank contaminated water. In freshwaters, some of the bloom-producing species of Anabaena, Aphanizomenon, and M i c r o c v d have been identified as major toxic strains. The toxins are of various types (alkaloids, polypeptides, pteridines, lipopolysaccharides) and have caused mortality of mammals, birds, and fishes, but no human deaths have been reported (Carmichael, 1981). Wheeler et al. (1942), stated that no human outbreaks of gastroenteritis have ever been traced to algal contamination of drinking water, and that it is probable that tastes and odors almost invariably associated with severe algal pollution would cause humans to seek other sources for drinking water before a harmful amount of the polluted water would be consumed. These authors state: "It should be noted that the presence of algae in drinking water, in addition to causing tastes and odors, may have some importance from the standpoint of the allergist as algae may, on occasion, liberate considerable amounts of protein in water. If allergic reactions to algae proteins do occur, they would be as uncommon as they would be obscure and hardly likely to occur as a public health problem." Schwimmer and Schwimmer (1955) chronologically summated 38 incidents of animal intoxications by phytoplanktonfrom 1878 to 1951. In most cases the attacks occurred after the animals had drunk from lakes or ponds containing heavy algal growths, usually during successive days of hot weather. The reported symptoms of algal intoxications vary but the most striking clinically were the involvements of neuromuscular and respiratory systems in cattle. Francis (1878) described the following symptoms: "the animals developed stupor and unconsciousness, falling and remaining quiet, as if asleep unless touched, when convulsions came on, with the head and neck drawn back by rigid spasm which subsided before death." The syndrome of symptoms described by Fitch et al. (1934) exhibited by guinea pigs from the feeding or from the inoculation intraperitoneally of a fatal dose of toxic algae was: (1) restlessness; (2) urination; (3) defecation; (4) deep breathing; (5) weakness in the hind quarters; (6) sneezing; (7) coughing; (8) salivation; (9) lachrymation; (10) clonic spasms and death. In studying experimental deaths of guinea pigs, it was noted that they occasionally show symptoms of intoxication and then recover. These reported symptoms closely resemble those typically shown in guinea pigs displaying severe anaphylactic shock, the violent allergic response or immediate hypersensitivity, known to be mediated by the production of large amounts of immunoglobulin E in response to a challenge dose of antigen administered to a previously sensitized animal (Barrett, 1983).

Gorham (1964) reviewed the literature on toxic algae as a public health hazard. He concluded that the fish and livestock poisons produced by waterblooms were nuisances and economic hazards rather than public health hazards. It was estimated that the oral minimum lethal dose of decomposing toxic Microcystis bloom for a 150-pound man would be 1 to 2 quarts of thick, paint-like suspension. Gorham stated that this amount would not be ingested voluntarily; however, in the case of an accident, such a quantity might be ingested involuntarily. Mackenthun and Ingram (1967) chronologically listed 20 outbreaks of human gastrointestinal disorders, 14 recorded human respiratory disorders, and 10 human skin disorders, all associated with algae.

All blue-green algae are not toxic. They are, however, very common and belong to a very ancient group of organisms. The fossil record indicates that blue-green algae existed and bloomed in ancient seas some 3 billion years ago. They are believed to have been responsible for producing large quantities of oxygen in the atmosphere, leading to atmospheric conditions appropriate for many other forms of life (Sze, 1986). Modern blue-green algae are found in all types of aquatic environments, capable of existing over a much broader range of environmental conditions and nutrient availability than eukaryotic green algae. Many of the planktonic bloom-producing species produce intracellular gas vacuoles which may cause their colonies or filaments to accumulate on the surface of the water as an unsightly scum. Eventually, the cells decompose on shore or in deeper waters as they sink below the surface, creating severe depletion of oxygen. Buoyancy of blue-greens may vary in response to

light intensity and nutrient availability (Spencer and King, 1985). As carbon becomes limiting, cells tend to rise (Klemer e t al., 1982). Availability of inorganic carbon for photosynthesis affects the development of gas vacuoles (Paerl and Ustach, 1982). Carbon dioxide and bicarbonate are the principal forms of carbon used for photosynthesis, and blue-greens cannot use carbonate at all. As the pH of the water increases, often as the result of photosynthetic removal of CO,, less CO, and bicarbonate a re available because the equilibrium among these carbon forms is changed. This results in reduced photosynthesis and increased vacuolation of cells. The cells rise to the surface where atmospheric CO, is available. Thus blue-greens may have a competitive advantage over other planktonic algae a t high pH because of their ability to layer at the air-water interface. The presence of extensive mucilage as a sheath around many blue-green algae is important in absorbing trace elements (Murphy et al., 1976). The mucilage binds trace elements making them available to the cells. This ability to bind trace elements may also give blue-greens a competitive advantage over other phytoplankton. Many blue-green algae, a s well as many diatoms, have the ability to "fix" atmospheric nitrogen. They do not, therefore, require other forms of nitrogen, like ammonia, or nitrate in water or sediments. This ability also contributes to the competitive advantage of blue-green algae, especially in conditions of limiting nutrients in natural ecosystems.

CONTROL STRATEGIES:

Nuisance algal blooms have been recognized in many rivers, streams, irrigation channels, ponds, lakes, and reservoirs. Exposure of water with any appreciable level of dissolved nutrients to direct sunlight inevitably results in the growth of algae. Excessive growth has created serious problems interfering with water resource utilization. A variety of methods has been developed that allow temporary reduction and control of plant nuisances under a number of circumstances. The type of control employed depends uon the nature and extent of the problem, the type and extent of control desired, as well as consideration of costs.

Mechanical harvesting, especially in shallow water environments, offers a direct and simple method of eliminating some types of rooted and/or filamentous plant pests and at the same time removing intrabiotic nutrients responsible for excessive plant growth. In practice, the technique has been limited principally to rooted vegetation in shallow impoundments. Physical disruption, dislodging and removal of algal mats in flowing waters would serve to remove algae and trapped nutrients from one site, but horizontal transport would only encourage trapping and accumulation at downstream sites, with broader dissemination of stream productivity. River flow, dilution by springs and tributaries, and total nutrient load should be carefully considered, as well as coordination of nutrient release with storm runoff and high flow to effectively remove nutrients and biomass with minimum effect on downstream sites. Merely harvesting nuisance plants, allowing them to decompose on the banks releasing trapped nutrients to be washed back into the river may only lead to subsequent, and perhaps even more serious plant growth. Seasonal algal blooms in nature are often short-lived phenomena, owing to periodic hydrologic events accompanied by effective scouring of the river bed, removal of excessive growth and dilution of released organic matter and nutrients. The most serious algal blooms seem to coincide with periods of low river flow and reduced horizontal transport.

The use of chemicals to control excessive growths of algae and aquatic weeds in lakes and reservoirs and irrigation channels has become widespread in recent years. However, chemical control of algal blooms in rivers has received little attention. In 1967, the British Columbia Research Council performed an extensive study of the market for algicides. The projected needs clearly indicates the major applications and estimates of the market for effective algicides. Those estimates included:

APPLICATION Municipal water supplies Irrigation 600 tons/year 15,000 tons/year Farm ponds 5,000 tons/year Red Tide Control Several Recreational waters hundred tons/year

5,000 tons/year Industrial Waters Small Swimming pools 300 tons/year amounts

This study, and others, indicate that copper compounds, principally CuSO,, is the dominant chemical used in large-scale treatments of public water supplies, irrigation and recreational waters, while more expensive chemical toxicants may have greater applicability in the small to intermediate scale market.

It is generally conceded that a good algicide or herbicide should: (1) be reasonably safe to use, (2) kill the specific nuisance plant, (3) be non-toxic to fish, fishfood organisms and terrestrial animals at the effective plant-killing concentration, (4) not be seriously harmful to the ecology of the general aquatic area, (5) be safe for water contact by humans or animals, (6) be cost effective. From 1904 (Moore and Kellerman, 1904) to the present, the chemical that has most nearly met specifications for the control of algae in large-scale aquatic impoundments has been copper sulfate (blue vitriol). Despite its extensive usage, copper sulfate has obvious shortcomings: (a) in excessive concentrations it may poison fish and other aquatic life, (b) it may accumulate in bottom muds as an insoluble precipitate following extensive application, and (c) it is very corrosive. Definite dosages of CuSO, for the control of various types of algae were first prescribed by Moore and Kellerman (1905) and reprinted extensively in tabuIar form with specific dosages for some 70 organisms (Hale, 1954). The solubility of copper in water is influenced by a number of factors, including pH, temperature, hardness, and alkalinity. In moderately hard to hard waters, 1 ppm CuSO, (pentahydrate) for the upper 2 feet of water (5.4 pounds of commercial copper sulfate per surface acre) is sufficient to control most common types of algae, if applied during early stages of algal growth. In soft water regimes, 0.3 ppm' (0.9 pounds per acre) is probably adequate for control. Soft water environments reportedly are most effectively controlled, with longer lasting effects, using copper sulfate.

De Vaney (1968) provided dosage rates and application procedures for a number of herbicides that have been registered in accordance with the Federal Insecticide, Fungicide, and Rodenticide Act for use in aquatic sites. These include:

Acrolein Irrigation Canals Ponds

Amitrole (Not approved for Bureau of Sport Fisheries and Wildlife use)

Non crop areas Drainage ditches

Ammonium Sulfamate Around lakes, ponds Around potable water reservoirs Along inflow streams

Bromacil Ditch lands (drainage)

Copper sulfate Farm ponds Lakes

Dalapon Non crop areas Drainage Ditches

Dichlobenil Lakes, Ponds

Dichlone Lakes, ponds Irrigation canalsDiquat Lakes, ponds Irrigation canals Drainage ditches

Endothall Lakes, ponds Irrigation canals Drainage ditches

Fenac Lakes, ponds Reservoirs Drainage ditches and banks

Petroleum Distillate (aromatic) Irrigation ditches Drainage ditches Irrigation, drainage ditches and banks

Silvex Lakes, ponds

Sodium Arsenite (Not approved 2,4-D for Bureau of Sport Fisheries Lakes, ponds and Wildlife use) 2,4,5-T

Lakes, ponds Lakes, ponds Sodium TCA

Non crop areas Ditch banks (drainage)

There are many things to be considered in the planned use of any algicide. Chemical control of aquatic vegetation must be regarded as a temporary remedy, especially in flowing water environments. Under certain conditions, the destruction of one particular type of algae or algal community may subsequently promote the development and growth of resistant forms or minor forms which may be just as objectionable as the original type. Satisfactory control may require repeated applications of algicide, especially in flowing waters, and especially in hard-water regimes. There is always the possibility of affecting aquatic life other than the nuisance plants. Exact effects on downstream communities, and partially diluted algicides are difficult to predict.

The use of biological controls, i.e. grazing organisms such as grass carp known to feed on the types of algae or other nuisance vegetation offers effective control in some situations. Likewise, many grazing organisms, from small single-celled protozoa to many larger worms, arthropods, and fish function in natural environments to limit the standing crop of aquatic vegetation.

Rather than seeking to inhibit growth of algae, some industrial operations have developed long, shallow meander systems for wastewater treatment, designed to encourage growth of photosynthetic organisms and remove many essential nutrients prior to the point of discharge. The meander system employed by the Doe Run Company's Buick Mine-Mill complex has been operating successfully for - 20 years (Gale, et al., 1974). In addition to ameliorating severe algal bloom problems in the receiving stream, Strother Creek, the abundant aquatic vegetation within the meander system has been shown to perform a useful role in removing vagrant heavy metals in the combined mine-mill wastewater stream.

RESULTS

Observations:

Tlie biological mats forming on the rocks of the West Fork of the Black River, especially noticeable during the summer months during periods of low river flow, are composed largely of algae, a community or mixture of varying proportions of filamentous green and blue-green algae together with single-celled varieties of green algae, desmids, and diatoms. The dark brown mats, often considered the greatest nuisance and most objectionable, are composed predominantly of stalked diatoms, with a diverse array of other diatoms and minor amounts of green and blue-green filamentous algae. The photosynthetic, autotrophic algae form the base of a very complex food chain, and many heterotrophic organisms are commonly associated with algal mats. Observed heterotrophs include many types of protozoa, insect larvae, annelids, nematodes, snails, and many bacteria.

Periodic algal blooms are common along the West Fork of the Black River and other regional streams throughout the year, encouraged and supported by appropriate temperatures and nutrient conditions. Even in the coldest months of the year, significant growths of the diatom Cvmbella can be found in many Ozark streams. Less commonly, an occasional bloom of green filamentous algae like S ~ i r - or Zyznema can be found in some of the warmer spring-fed streams. Algal blooms are usually more noticeable, even reaching nuisance proportions, during the warm summer months, from late May or early June until the onset of cold weather, usually in October or early November. Particularly heavy algal blooms are often seen early in the spring, when the onset of warm weather and normal spring runoff allows microbial decomposition of leaves and debris, with concomitant release of trapped nutrients. This often occurs in advance of later blooms of consumer organisms that may reduce the standing crop of algae, even though growth rates may remain high. Appreciable blooms may occur periodically throughout the summer and again in the fall, as combined circumstances of nutrient availability due to increased microbial degradation and appropriate temperatures encourage rapid growth of some forms of algae. Algal communities, like terrestrial communities, may undergo considerable seasonal change, as normal succession patterns develop.

On many occasions during the course of the present study, visits were made to the primary sampling sites along the West Fork of the Black River as well as many other regional streams and rivers. A number of television tape recordings were made to document general river conditions and microscopic observations performed on algal samples. Summarizing comments were often included in weekly or monthly reports sent to Mr. Owsley. Comments included in the report dated 18 July 1991 are of particular interest, since they describe river conditions during a typical summer algal bloom: Excerpts from the report on that occasion follow:

O n J u l y 14th I v i s i ted a l l our s i t e s o n t h e W e s t Fork a n d B i l l s Creek a n d co l l ec t ed algal samples f o r i d e n t i f i c a t i o n . O n that date I a l s o col lec ted water samples f r o m several springs, i nc lud ing t h e l i t t l e spring located i n t h e W e s t Fork near t h e bank o p p o s i t e t h e minewater discharge. I be l i eve t h e data f r o m al l t h e s e springs serve a s u s e f u l compar i sons and provide assurance that natural underground waters con ta in s ign i f i can t l eve l s o f n i t rogen and p h o s p h o r u s , t h e t w o m o s t critical n u t r i e n t s f o r growth of algae and aquat ic p lants i n sur face waters. T h e elevated concen t ra t ions of i ron and manganese in that l i t t l e spring are, I a m c o n f i d e n t , largely r e spons ib l e f o r m u c h o f t h e dark brown and black "gunk" o n t h e r iver b o t t o m f o r s o m e d is tance downs t ream.

O n t h i s occas ion , ex t ens i ve algal b l o o m s were ev iden t all a long t h e W e s t Fork of t h e Black River. A s y o u k n o w , water l eve l s are l o w t h i s t i m e of year a n d t h e current i s c o m m o n l y s low . M u c h of t h e earlier b l o o m of t h e

l igh t brown d ia tomaceous ma t ( C v m b e l l a ) has n o w been replaced b y bright green f i l a m e n t o u s algae a t many s i t e s a long t h e river. T h e major algal f o r m s i d e n t i f i e d f r o m samples co l l ec t ed o n 7 / 1 4 / 9 1 are as f o l low:

S i t e # I : Ex tens i ve coverage o f b e n t h i c region and accumula t ion o n rocks and i n p o o l s by t h e green f i l a m e n t o u s algae S p i r o ~ w and a ~ n e m q , with many m i n o r d ia tomaceous f o r m s . L i t t l e or n o mat f o r m a t i o n e v i d e n t o n b e n t h i c r o c k s . Occas ional ly , green algae were very d e n s e a long t h e banks , a long ent i re length o f r iver.

S i t e #2: Occas ional d e n s e patches o f green f i l a m e n t o u s algae S ~ i r o p - , Z v ~ n e m a , and cons iderable M o u ~ e o t i a , t h roughou t gen t l y f l o w i n g r i f f l e z o n e s and p o o l z o n e s . Especia l ly abundan t a long edges o f creek . L i t t l e or n o mat f o r m a t i o n .

S i t e #4 : Appearance o f t h i s s i te changes very l i t t l e t h roughou t t h e course o f t h e y e a r . Pers is ten t , t h i n algal ma t , wi th a variety o f f i l a m e n t o u s blue-green algae, i nc lud ing Oscil latoriq. T h e f ragile green f i l a m e n t o u s M o u ~ e o t i g was abundan t o n t h e very sur face o f t h e algal ma t . W i t h i n t h e tangled f i ber s o f t h e mat i t s e l f , t here was a n impress i ve array o f various d i a t o m s o f m a n y genera, s o m e s ta lked and s o m e unat tached. T h e s e inc luded As t e r ione l lg , JVavicula, C v m b e l l s , F r a ~ i l l a r i g , G o m ~ h o n e m a , and m a n y o ther m i n o r cons t i t uen t s .

i t e #5: T h i s broad, shal low area o f t h e r iver had obv ious l y b e e n stirred u p A T V ' s , a n d / o r o ther o f f - t h e - r o a d veh ic l e s . T h e rubb ly b o t t o m o f t h e

s tream was q u i t e c l ean- -much cleaner than s t re tches o f t h e r iver ups tream a s 11 a s downs t ream. V e r y sma l l patches o f t h e d ia tomaceous m a t s c o m p o s e d

largely o f C v m b e l l g were f o u n d , b u t t h e s e were n o t present i n " b l o o m " quant i t ies or d e n s i t y because o f o b v i o u s vehicular t r a f f i c w i th in t h e s tream. W i t h i n a f e w yards downs t ream, t h e algal b l o o m was again apparent . L i t t l e or n o mat f o rmat i o n .

S i t e #6 : Ex tens i ve b l o o m s o f algae observed . T h e green, f i l a m e n t o u s f o r m s S p i r o ~ v r g , a p n e m a , and Moupeo t ia were abundan t , a t a b o u t t h e same nu i sance l eve l s or d e n s i t y a s seen a l l a long t h e river ups t ream of Highway K K . Occas ional patches o f very d e n s e algal ma t c o m m u n i t i e s . T h e major c o n s t i t u e n t o f t h e s e d e n s e d ia tomaceous m a t s was t h e s talked Cvrnbellq. Many o ther m i n o r d i a t o m cons t i t uen t s .

Near S i t e #7 , i n t h e river a t p o i n t o f discharge: Water l eve l s were l o w , water warm a n d clear w i th in t h e ma in stream a b o v e indus tr ia l discharge. Large patches o f green f i l a m e n t o u s algae S n i r o p y u , Z v ~ n e m a , and Moupeo t iq wi th in ma in river channe l . T h e s e patches c o n t i n u e d downs t ream of t h e indus tr ia l discharge. T h e discharge i t s e l f was sl ight ly turbid a n d coo le r than t h e rece iv ing water o f t h e r iver. T h e s o u t h b a n k at and b e l o w t h e discharge po in t had ex t ens i ve roo ted vegeta t ion , with f l oa t inggreen f i l a m e n t o u s algae trapped a m o n g t h e plants a long t h e shady shore . T h e ex tent and t y p e o f algal growth , however , was s imi lar t o that seen a t m a n y s i tes ups t ream.

T h e nor th s ide o f t h e r iver was s u n l i t , popula ted by larger roo ted plants . A large, dry gravel bar d i v ided t h e s t ream. T h e ma in river channe l and c o m b i n e d indus t r ia l discharge f l o w e d a long t h e s o u t h s ide o f t h e gravel bar.

T h e nor th s ide was o b v i o u s l y more e levated , shallower, and m u c h colder , wi th o b v i o u s upwel l ing o f water and occas ional gas b u b b l e s f r o m a spring. W i t h i n t h e spring area and downs t ream, and al l a long t h e gravel bar where t h e spring water was emerging and s o m e t i m e s percolat ing th rough t o join t h e ma in current , t h e rubb ly b o t t o m was d i sco lored , probably d u e t o precipi tated ferr ic and manganic materials . Algae growing wi th in t h e spring area and percola t ion areas o f t h e gravel bar were o f t e n d i sco lored and covered with t h e same f err ic /manganic depos i t s . S p e c i m e n s o f algae w i th in t h e spring region inc luded: t h e f i l a m e n t o u s green S p i r o g u , Z v g n e m a , and

e o c l o n i u m , and t h e f i l a m e n t o u s b lue-green Oscil latorig and o ther very smal l -d iameter f i l amen t s t hough t t o be b lue-green algae. A spectacular array o f d i a t o m s accompan ied t h e green and b lue-green f i l amen t s . major d ia tom c o n s t i t u e n t s i n c l u d e d : Cvmbell_a, 5;0mphonema, F r a ~ i l l a r i g , As ter ionel lg , and N a v i c u l ~ .

S i t e # 9 , t h e Grand Daddy Ho le : O n t h i s occas ion , t h i s region o f t h e r iver ac tual ly appeared cleaner, wi th l e s s o f an apparent algal b l o o m than many ups tream s i tes . Cons iderab le roo ted vegetat ion along t h e rocky east bank , w i th l i t t l e trapped f loat ing algae. L i t t l e or n o ev idence o f mat f o rmat ion . S o m e water hyac in th a long t h e east bank . Occas ional patches o f a lgalgrowth were apparent . T h e major c o n s t i t u e n t s i nc luded: S p i r ~ g y ~ g and m i n o r quan t i t i e s o f Osci l latorig, a s well a s n u m e r o u s d ia toms , and G o m ~ h o n e m a and o ther m i n o r cons t i t uen t s .

W i t h i n a half m i l e downstream o f t h e Grand Daddy H o l e , t h e rubb ly b o t t o m o f sha l low r i f f l e z o n e s was comple t e l y covered by a dark brown algal mat . T h e c o n s t i t u e n t s were t h e same as t h o s e seen ups tream, wi th abrupt changes i n relat ive abundance . Whereas t h e green f i l a m e n t o u s algae were m o r e abundan t ups tream, rhe predominan t f o r m s became C ~ m b e l l g and associa ted brown d i a t o m s which c o m p l e t e l y covered t h e submerged r o c k s a n d rubble .

W e are, a s y o u have u n d o u b t e d l y s een , i n t h e m i d d l e o f an ex tens ive algal b l o o m o n t h e W e s t Fork o f t h e Black River . I t s h o u l d be somewhat reassuring that t h e b l o o m i s n o t just be low t h e minewater discharge poin t . T h e algae are n o t weird or unusua l f o r m s . T h e r e i s an o b v i o u s change i n t h e relat ive abundances o f t h e s e algae, resul t ing i n a darker, f i rmer algal mat , and s o m e d i sco lora t ion o f t h e r o c k s f o r s o m e d is tance downs t ream o f t h e Grand Daddy H o l e . R igh t n o w , t h e Grand Daddy H o l e i t se l f l o o k s pretty g o o d , wi th t h e worst appearance s o m e d i s tance downs t ream. J u s t what t h e relat ive c o n t r i b u t i o n s are o f indus tr ia l discharge, t h e smal l spring, local geography, hor i zon ta l transport o f nu t r i en t s wi th in t h e r iver and f r o m adjacent l and , and natural success ion caused by growth o f t h e algae t h e m s e l v e s , i s d i f f i c u l t t o sort o u t .

Generally, within the West Fork of the Black River during the course of the present study, major algal blooms have been observed along the entire river basin, upstream and downstream of the ASARCO mine-mill complex. At times, these algal blooms have reached nuisance proportions at several locations, especially evident at sites #1, #2, #4, #5, #6, #9, #lo, and #11. Commonly observed components of algal blooms upstream of the Highway KK bridge include Qm!&h, especially during colder months and during early summer, SDiroevra and m, especially common during warm weather, with minor quantities of m, Oscillatoria, and many other minor diatoms. Dense algal growth has also frequently been observed, especially during the warm summer months at

periods of low stream flow, downstream of the ASARCO industrial complex. Deep pools and slow- flowing regions like the Grand Daddy Hole act a s effective traps for nutrients and debris. Successional patterns observed at upstream sites a re also seen downstream. Blooms of C v m b e k are commonly followed by blooms of SDironvra and m, as well a s the more fragile M o u w . But, unlike most upstream sites, the stalked diatoms, Cymb& and Gom~honema , the non-stalked Tabellaria, Asterionella, Navicula, together with the blue-green filamentous -, seem to persist and provide a protective environment that encourages the development of an impressive and diverse community of diatoms and associated microscopic consumer organisms. Dense growth of diatoms often contributes to a brown-colored, slimy coating that effectively covers the entire benthic region, and extending 2-3 miles downstream. Temperature, nutrient availability, horizontal transport of materials, river flow conditions, grazing organisms, and excreted metabolites all influence the extent, composition, accumulation, and persistence of benthic communities.

The severity and extent of algal blooms in Ozark streams may vary from year to year. The blooms of summer, 1990 were much more obvious and objectionable than those of 1991. Nutrient availability, weather conditions, river flow conditions, successional patterns brought about by many

. complex and interdependent factors and timing, make predictions difficult.

DISCOLORATION O F ROCKS AND ABRUPT CHANGE IN APPEARANCE O F RIVER NEAR INDUSTRIAL OUTFALL

Part of the problem of discoloration and abrupt benthic community alteration near the discharge of the ASARCO mine pond effluent is undoubtedly due to the emergence of a sizeable sprin on the north side of the river m e bed ' oond discharge channel. Similar, thoughg smaller springs emerg% in the vicinity of the mine pond discharge channel and a short distance west (upstream) of the discharge channel on the south bank. The influence of this un-named spring is indicated in Figure 2. The sketch was made from field notes taken on September 21, 1991, at which time a portable conductivity meter was used to determine conductivity and temperature of river water. Conductivity readings were particularly high in those shallow areas where upwelling was obvious and the rocks were intensely stained. These springs have been found to contain significant quantities of iron and manganese which quickly oxidize and precipitate out on the rocks and vegetation. The dark surface stain appears t o have a particular affinity for chert rubble. The blackened surface stain on rock specimens taken from the West Fork of the Black River and other regional streams was the subject of a separate study by Gale and Patterson (1992). The black surface coat consists largely of MnO,, often associated with co-precipitated ferric salts, and is easily removed by elution with concentrated HCI or, other reducing agents. Induction-coupled Argon Plasma spectrometry of such eluates has shown the presence of large amounts of manganese, together with varying amounts of several other accompanying metals. Table 3 contains the results of ICP analyses performed on diluted samples of HC1 eluates of blackened rock surfaces. The rock specimens included:

WF-SP Black Rock taken from un-named spring in West Fork WF-SB Black Rock taken from bank near un-named spring BC-BR Black Rock taken from Brushy Creek Minewater discharge channel WF-DS Black Rock taken 25 yards downstream from spring in West Fork WF-GL Black Rock taken from dry gully near spring in West Fork WF-DR Black Rock taken from West Fork River bank 1% miles downstream from spring WF-SW Black precipitate taken from plastic container used to hold spring water

sample (held approx. 1 month in laboratory)

The manganese content of the blackened surface coat materials ranged from 26 to 76% of all elements detected by ICP analysis. Iron content ranged from 4.38 to 39.25%. Manganese and iron, shown to be present in elevated quantities in the emergent spring and in the darkened surface stains of benthic

rocks and organisms are known to have profound effects on algal community structure. They, together with cooler stream temperatures have been cited by Patrick et al. (1969) a s responsible factors fo r encouraging the growth of diatoms rather than green filamentous forms.

The black surface coating found on rocks in the West Fork of the Black River is found in many regional rivers and streams, a s well as the industrial discharge channels of the New Lead Belt. The black coat material is composed largely of manganese, probably MnO,. Minor amounts of co- precipitated Fe, Co, Cd, Pb, and Z n have been found associated with the black surface coat, but the predominant material present is manganese. The black manganese coating of benthic rocks occurs when underground waters containing significant quantities of soluble manganous (11) materials a r e brought to the surface. In an oxidizing environment, at neutral or alkaline pH, the manganese is quickly oxidized to the quadrivalent state and forms stable, insoluble oxides. The black manganese deposits often occur in close proximity to red, ferric deposits. Iron and manganese are known to be closely associated. The black surface coating material is easily dissolved and removed from rock surfaces by concentrated HCl or reducing agents such a s dilute sulfurous acid or sodium hydrosulfite. Manganese is a known biological nutrient (micronutrient), essential for plant photosynthesis and growth. It may, under some conditions and moderately elevated concentrations, stimulate stream productivity or act a s an environmental factor encouraging the growth of certain types of algae, especially diatoms. It may be effectively trapped and bound within algal mats, along with other heavy metals. Biological communities may compete for available manganese, and participate actively in the biogeochemical cycling of manganese in natural ecosystems. In reviewing the biogeochemistry of manganese, it becomes evident that this element has great mobility in the natural environment. Because of its unique redox and solubility properties, and the relative stabilities of possible species in the natural environment, manganese is constantly being cycled behveen biotic and abiotic components. It is commonly cycled between oxygen-rich epilimnetic waters and oxygen-depleted hypolimnetic regions by interacting biological and geochemical processes. Under anaerobic, mildly reducing aquatic environments, like those found in deep pools, it may be reduced and solubilized, leached from one area, then redeposited in other areas as subtle changes in pH and redox occur. Manganese is a very common constituent of rocks and soils. It is especially abundant in Pre-Cambrian and Recent rocks and derived residuum in southern Missouri. The New Lead Belt is located within a manganiferous region where many blackened rocks display geochemical evidence of its ubiquity and continual biogeochemical cycling. It is obvious that manganese was concentrated in regional sedimentary rocks by geochemical processes of the past. It is also obvious that manganese is geochemically mobile and has been leaching from regions of dense deposits exposed to water. Mining and milling certainly accelerate the leaching process by fracturing manganiferous rocks and exposing them to water. Underground water, whether in a mine or natural aquifer, may bring dissolved manganous salts to the surface. Because of the geochemical properties of surface streams, soluble manganese (11) is quickly oxidized and precipitated. Localized deposits of manganic (IV) materials may be mobilized under mildly acidic conditions, especially a t low oxidation potentials. (Gale and Patterson, 1992)

F i g u r e 2 . 21 S q t e n b r 1991: CCWUXIVITY 6 TFWEWKW3 -S Centigrade 411 - 1

Table 3. ICP Analyses of Surface Haterial on Blackened Rocks

WF-SP

3.600

,200 7.610

120

2

60.200

.640

24.100 456

4.600 .690

3.600 1.200

1.400

.370

.056

.070 ,880

687.216

WF-SB

18

14.300 .008

63

1.500

.loo 142

.730

35.500 558 .070 7.900 ,990

3 3.600

2.200

.270

.520

.290 1.900

853.878

% BC-BR 0

2.11 46.100 0 3.400 0 .200

1.67 3.110 .OO .032 0

7.38 7 09 0 .430

.18 53.900 0 .540

.01 4.500 16.63 381

0 .09 6.800 0 .040

4.16 89.400 65.35 67 8 .01 .070 .93 4.400 .12 '47.200 .35 5.700 .42 322 0 .600 0

.26 10.900 0

.03 1.300

.06 .610 0

.03 .840

.22 218 100.00 2588.072

WF-DS

53.800

11.300 .034

17

16.900

2.200 40.200

.680 1.400 7.300 545 .080

2.100 2.100

1 8.500

1.800

.I20

.350

.330 2.400

714.594

WF-DR

22

7.900 .016

230

1.100 .loo .loo 261

.470

58.700 359

11 .940

7.500 2.100

3

.270 ,890

.440 1.500

968.026

WF-SW

1.700

.704

16

.300

82

.loo

6.100 .93

2.900 -200

2 .800

1.700

.065

.069

1.300 208.938

RESULTS OF ROUTINE CHEMICAL ANALYSES O F WATER SAMPLES

The results of routine analyses for N03-N, NO,-N, Phosphate-P and NH,-N a re shown in Tables 4-7. Raw data and graphical presentations of accumulated data for each site are included in Appendices A through D. A separate series of graphs is presented in each Appendix where nutrient concentrations are plotted against time (week of collection) and computer statistical software was used to construct the best linear fit of the data as a function of time. Significance of slopes sometimes seen in such plots of best linear fit is difficult to assess. To minimize possible influence of outlying data points, simultaneous plots are included for each site using running median analysis. This common procedure considers the data in clusters of 5, plotting the value of the median in each cluster, rather than each individual data point. The summary data in Tables 4-7 include arithmetic means and standard deviations of the mean obtained from respective nutrient concentrations at each site. The simple correlation coefficient (r) is an indication of how well the data conform to the straight line attempting to correlate nutrient concentration with time (week of study). Regression analyses and robust regression analyses comparing nutrient concentrations versus time were done to determine if observed slopes were significant. The shape and slope of running median plots shown in the Appendix offer additional corroborative evidence of significance. Probabilities shown in Tables 4-7, when < 0.050 (at the 95% confidence level) and especially when robust probabilities, derived by statistical techniques applied to minimize effects of outliers are also low (<0.050), a re highly suggestive that the slopes are real and one can be reasonably confident that values are either dropping or rising over time. It would appear, therefore, that decreasing nitrate concentrations at sites #7 and #10 are strongly indicated, and those at site #8 are marginally indicated. On the other hand, nitrate concentrations appear to be increasing with time a t site #3, though the evidence is only marginal. Decreasing concentrations of nitrite a t sites #7 and #8 are also strongly indicated. Similarly, the evidence is fairly strong that ammonia concentrations are decreasing at sites #7 and #8. A decrease in ammonia concentrations at sites #2 and #4 is, perhaps, suggested as well.

For many of the water samples collected during 1991, analyses were conducted to determine conductivity (pSiemens/cm), total dissolved solids (TDS, as mg/l), Alkalinity ( mg/l as CaCO,), Hardness (mg/l as CaCO,), and pH. The results of these chemical and physical analyses are presented in the Appendix for the eleven primary sites. A summary of these ancillary water quality data for the eleven primary sites is presented in Table 8.

At various times during the course of the present study, samples were taken at various additional sites for purposes of comparison. Included in these extra samples was a number of regional springs and additional industrial discharge waters. The results obtained from analyses performed on these non-regular samples are shown in Table 9. On some occasions, to provide same-day comparisons, an extra non-regular sample was also collected from one or two of the regular sampling sites. These data are also shown in Table 9.

Exceptionally high concentrations of phosphorus and nitrate-N were observed in samples taken from Love Creek and Little Beaver Creek near Rolla. Samples were taken a short distance downstream from sewage treatment plant effluents, and both these streams display periodic heavy algal blooms. Elevated nitrate-N levels were consistently found in most of the springs tested, as well as in all industrial underground water discharges tested. These results indicate clearly that the underground waters (aquifers) in the entire region have a significant background level of nitrate-N, often between 0.5 and 1.0 ppm. Minewater discharges often contain twice to three times as much nitrate. It is not clear whether the increased nitrate concentrations in minewater result from simple exposure of nitrate- bearing rocks to percolating water, or whether some of the nitrate comes from the ammonium nitrate/fuel oil mixture commonly used as blasting material.

The un-named spring in the West Fork of the Black River bed directly across from the ASARCO minewater discharge point showed somewhat elevated nitrate-N on only one occasion out of six samples recorded in Table 9. On the other hand, this spring consistently showed very elevated levels of ammonia-N, a s well as very high conductivity, total dissolved solids, and hardness.

TABLE 4.

Nitrate concentrations are highly variable. Several of the river sites display a consistent pattern of elevated nitrate concentrations during the cold fall and winter months when algal growth is restricted. This pattern is consistent with

? decomposition of deciduous leaf litter and runoff during periods when biological uptake and utilization is limited. b

Mean concentrations of Nitrate-Nitrogen at sites #4, #7, and #8 are obviously above the 0.3 ppm level recommended to avoid nuisance algal growth. Mean concentrations of Nitrate-Nitrogen at sites #2, #9, and #10 are close to the recommended level. The influence of industrial discharges is obvious. However, it is important to recognize that the indus~rial discharges from the Brushy Creek Minewater Pond and the ASARCO West Fork Minewater pond consist largely of underground water which may be expected to contain some natural background levels of nutrients. Natural springs, far removed from New Lead Belt mining operations also contain significant quantities of nitrates. Several

crease in the concentration of nitrate- rease in Nitrate-Nitrogen levels at Site

, . . . L\ch.?c,, :,-L.) < * '-& &.-Z<C .-

- ,.' q ) -::-:-:.. , ! J h . C - . i , - .:,,; , **-, A,'.

F'A ,&*&.: :..- , ~1,. ,--3 r k ?&. ,I. -3.l. j;,, :.: ,

. : /Iq .'*;>-j 2 . . .. '*. . -- -. . , . / . - . . - . . " d ! : : . 7 , . , , , ,* 2

,c,1.: ' -.c

( - _ _ . , . ! \ ! ; 1 . / ,$q['L;1 . ! I . ? /:.I- . I ?-

? ? . * . . ..

NITRITE NITROGEN

Nitrite-Nitrogen concentrations are generally very low, as would be expected in these highly aerated waters. Slightly elevated levels a t site #7 and site #8 probably reflect the intermediate stage in oxidation of ammonium ions, present in ammonium nitrate used in underground explosives.

SAMPLING SITE

1. W.F. Northwest

2. Bills Creek @ Crossing

3. Bills Creek @J Tailings

4. Brushy Creek Mine Pond

5. W.F. Below Bills Creek

6. W.F. @ Old Hwy

7. W.F. Mine Pond

8. W.F. Mine Pipe

9. W.F. Grand Daddy Hole

10. W.F. 1.5 Miles Down

11. Mill Branch

MEAN

0.0003

0.0005

0.0007

0.0030

0.0006

0.0007

0.0709

0.1190

0.0035

0.0023

0.0006

STD DEV

0.001

0.001

0.002

0.003

0.001

0.001

0.022

0.052

0.002

0.001

0.001

r

-0.056

-0.031

-0.052

0.035

0.074

-0.003

-0.454

-0.353

-0.045

-0.285

0.067

PROB

0.750

0.860

0.768

0.841

0.674

0.987

0.006

0.037

0.800

0.097

0.700

2

ROBUST PROB

- - -- - -

- -

- -

- -

0.0001

0.0068

0.382

- -

--

25

TABLE 6. PHOSPHATE PHOSPHORUS

Mean phosphate concentrations at all eleven primary sampling sites were well below the 0.1 mg/l level recognized as conducive to nuisance algal blooms. Several sites, however, displayed mean phosphorus concentrations in excess of the 0.009 mg/l recognized as definitely limiting to algal growth. It should be stressed that the dissolved phosphate

- '1 analyses routinely conducted may not accurately reflect the total phosphorus available within the biota or benthic

, sediments. The literature contains estimates of 1.8 - 3.3 pounds of phosphorus per acre of forest which may be ' contributed to aquatic ecosystems. The upper West Fork of the Black River drainage basin contains approximately 48,000 acres of deciduous forest, in addition to several residences, and farms with numerous cattle, goats, horses, and other domestic animals. The forest alone could contribute 1.8 X 48,000 = 86,400 pounds of phosphorus per year up to 3.3 X 48,000 = 158,400 pounds of phosphorus per year to the river and its tributaries. According to literature estimates based on an average phosphorus content of 0.7% (wet weight basis), this could translate into 1450 pounds of algae per pound of phosphorus, amounting to 125 - 230 million pounds of algae per year distributed, of course, along the entire river. The relative contribution of the ASARCO West Fork minewater pond discharge may be estimated as follows:

Average Flow = 1200 gpm, or 1.728 mgd. Mean content of 0.024 mg/l P X 8.345 = 0.2 pounds of P per million gallons 1.728 mgd X 0.2 pounds per million gallons = 0.346 pounds of P per day 0.346 X 365 = 126.3 pounds of P per year.

Theoretically, each pound of P could translate into up to 1450 pounds of algae (wet weight). This single industrial discharge could contribute to the growth of up to 502 pounds of algae per day or 0.183 million pounds of algae per year, distributed horizontally along the rivers between the mine and the Gulf of Mexico and beyond. By comparison, runoff from the surrounding forest in this watershed probably contributes 600 to 1200 times the nutrients or the resultant algal growth contributed by this industrial discharge. Such calculations are of limited predictive value, since

I

the nutrients like phosphorus are constantly subject to precipitation, variable horizontal transport, loss to deep sediments, biological food chain transport, incorporation, and sometimes storage.

A comparison between the industrial discharge and the main river would indicate that the concentration of phosphorus in the minewater discharge is approximately 2.67 times that in the river, while the total flow of the river is approximately 10-30 times that of the industrial discharge. There is, therefore, considerable dilution.

SAMPLING SITE

1. W.F. Northwest

2. Bills Creek @ Crossing

3. Bills Creek @ Tailings

4. Brushy Creek Mine Pond

5. W.F. Below Bills Creek

6. W.F. @ Old Hwy

7. W.F. Mine Pond

8. W.F. Mine Pipe

9. W.F. Grand Daddy Hole

10. W.F. 1.5 Miles Down

11. Mill Branch

MEAN

0.0086

0.0061

0.0097

0.0080

0.0075

0.0090

0.029

kJd 0.0139

0.0178

STD DEV

0.014

0.012

0.014

0.011

0.011

0.015

0.021

0.016

0.011

0.018

0.027

r

0.163

-0.124

-0.001

-0.093

0.279

0.198

-0.105

0.212

0.119

0.112

0.415

PROB

0.350

0.4769

0.998

0.595

0.105

0.254

0.550

0.222

0.496

0.522

0.013

ROBUST PROB

--

0.752

0.763

0.633

0.002

0.724

0.198

0.006

0.67 1

0.943

0.009

TABLE 7

-1 AMMONIA NITROGEN

- 1 Under aerobic conditions in soil, sediments, o r aquatic environments, ammonia is oxidized to nitrite and then

1 to nitrate by chemoautotrophic microorganisms (Nitrosomonas and Nitrobacter). Blue-green algae and many diatoms can readily utilize inorganic nitrogen compounds, including nitrate, nitrite, and ammonium salts. Some, but not all species, can also assimilate elemental nitrogen (N,) from the atmosphere.

Elevated levels of ammonia a re toxic to many aquatic animals. In fish, ammonia toxicity is accompanied by hyperplasia and reduced efficiency of gills, reduced activity, reduced stamina and growth, alteration of blood, liver. and kidney tissues, diuresis, and increased oxygen consumption.

SAMPLING SITE

1. W.F. Northwest

2. Bills Creek @ Crossing

3. Bills Creek @ Tailings

4. Brushy Creek Mine Pond

5. W.F. Below Bills Creek

6. W.F. @ Old Hwy

7. W.F. Mine Pond ( 8. W.F. Mine Pipe

9. W.F. Grand Daddy Hole

10. W.F. 1.5 Miles Down

11. Mill Branch

MEAN

0.038

0.057

0.052

0.101

0.046

0.045 f [

'0.661

\, 1.12

0.065

0.040

STD DEV

0.036

0.057

0.058

0.071

0.034

0.043

0.287

0.740

0.060

0.056

0.035

r

-0.072

-0.287

-0.019

-0.241

-0.073

0.091

-0.497

-0.357

0.085

-0.092

-0.087

PROB

0.683

0.095

0.914

0.163

0.678

0.605

0.002

0.035

0.626

0.598

0.619

ROBUST PROB

0.463

0.046

0.790

0.143

0.431

0.787

0.000

0.028

0.932

0.224

0.665

TABLE 7A.

7 The following data, taken from Balarin and Haller (1982) give some guidance on water quality requirements for survival and growth of various fish, including Tilapia, Carp, Channel catfish, and trout under culture conditions (mass aquaculture):

' Level at which growth is affected. An attempt has been made here to delineate environmental tolerance limits but these are by no means fixed and can vary and interact with other water quality parameters,

- I e.g. total ammonia toxicity varies with pH.

1 Tabulated chronic and acute criteria for total ammonia promulgated by the Missouri Department of Natural Resources Clean Water Commission for General Warm-Water Fisheries are reproduced in the Appendix. The concentrations of ammonia observed in the ASARCO minewater discharge fall within permissible levels established for the range of temperature and pH encountered.

-

Parameter

Temperature ("C)

Salinity tolerance (%)

Critical Oxygen (mg/l)

PH

Lethal Ammonia levels Total (mg/l) NH,-N (mg/l)(unionized)

Turbidity tolerance (mg/l)

Lethal CO, conc. (mg/l)

Nitrite tolerance limit (D,)

Tilapia

8-42

< 20-35

0.1-3.0

4.0-11

> 20.0 2.3 (0.5)'

13000

>73.0

2.1

Carp

6-40

c 12.5

3.0

4.5-12

10-13

> 190

Channel Catfish

1-34

3.0

6.5-8.5

(0.13)'

> 25.0

c 7.55

Trout

2-23

c 15

4.0

4.6-9.5

> 2 0.35 (0.1)'

> 15

(15-20)'

0.19 (0.015)'

Max. Tolerable Level

5.0

6.85

0.1

15.0

22.0

0.1

T a b l e 8.

SUMMARY OF ANCILLARY WATER QUALITY DATA PRIMARY SAMPLING SITES

* Tabulated data indicate MEAN f Standard Deviation n = number of individual water samples from each site

SITE

1

2

3

4

5

6

7

8

9

10

11

n

COND ~rS/cm

328 f 35

456 f 44

411 k 38

540 f 36

363 f 39

348 _+ 39

452 f 11

471 f 18

376 f 53

342 f 30

309 f 34

14

TDS mg/l

164 f 18

228 f 22

206 f 18

270 f 18

182 f 20

174 f 19

226 f 5

236 f 9

188 f 26

171 f 15

155 f 17

14

ALK mg CaCO,/l

168 f 22

177 f 7

210 f 22

169 f 8

164 f 15

160 f 15

164 f 2

168 f 4

157 f 14

157 f 13

154 f 16

11

HARD mg CaCO,/l

171 f 20

214 f 16

217 f 21

233 f 15

179 f 17

172 f 19

189 f 6

195 f 9

180 f 23

171 f 15

159 f 17

11

PH Range

7.43-8.29

7.35-8.30

7.01-8.15

7.74-8.56

7.46-8.15

7.58-8.15

7.62-8.24

7.32-8.20

7.16-8.12

7.34-8.29

7.54-8.35

12

T a b l e 9 . W a t e r Q u a l i t y D a t a f r o m A d d i t i o n a l S a m p l i n g S i t e s

-. SITE DATE

, 19 Grand Daddy Hole 12/02/90 Alley Spring 03/17/91 "Bee Pork @ BWY Tl' 06/28/90 Current Biver @ Akers 11/25/90 Doe Bun 129 nine 06/28/90 Fletcher nine Pond 11/06/90 Fletcher nine Pond 06/28/90 Fletcher Hine Pond 10/06/90

I Indian Qeek @ Courtois 06/28/90 -4

Lane Spring 11/25/90 Lane Spring 02/18/91 Lane Spring 03/17/91 Lane Spring 06/09/91

06/23/91 07 114 I91

Little Beaver Creek 11/25/90 -- Love Creek 11/25/90

Love Creek W06/90 Love Creek 06/24/91 Love Creek 06/26/91 Love Creek 07J15)91- . .

Hartin Spring 11/25/90 Heranec spring 11 11/25/90 Heranec Sprinq 12 11/25/90 Hontauk Spring 02/18/91

- r Hontauk Spring 03/17/91 , Hontauk Sprinq 06/09/91

Hontauk Sprinq 06/23/91 Hontauk Spring 07/14/91 Hontauk Sprinq 11 11/25/90 Hontauk Sprinq 12 11/25/90 Hontauk Spring 13 11/25/90 Neals 11 Upstream 11/06/90 Heals 13 Dovllstream 11/06/90 Spring in WF aver Bed 08/19/90 Spring in WF River Bed 10/06/90 Spring in WF River Bed 12/02/90 sprhq in WF River Bed 06/12/91 Spring in WF River Bed A07/14/91 Spring in WF Biver Bed B07/14/91 Strother Creek 11/06/90 Sweetwater Discharge 11/06/90 Welch Sprinq 11/25/90 Welch Spring 06/09/91 Welch Spring 06/23/91 Welch Spring 07/14/91 WF nine Discharge 11/06/90 WF h e Pond 08/19/90 W nine Pond @ River 12/02/90 WF Opstrear, of Sprinq 08/19/90

STREAM FLOW DATA

Stream flow on the West Fork of the Black River and the West Fork minewater discharge channel are routinely monitored by ASARCO personnel. Available data for 1990-91 are shown in Table 10. These data indicate that flow from the minewater pond remained relatively constant, ranging from 1.33 to 2.28 mgd in 1990, and from 0.83 to 1.11 mgd in 1991. There was a significant drop in the 6 volume discharged at the end of 1990. Measured flow in the main river channel ranged from 10.48 mgd to 45.73 mgd, with several periods when flow rates were above instrument limits or when excessive flooding required removal of monitoring equipment. The recorded data indicate that periods of lowest flow occurred during the summer months of both years, providing the ambient conditions conducive to summer algal blooms in the West Fork. During such periods of low flow and low dilution, nutrients from limited runoff, natural decomposition, springs, or industrial waters may approach maximum availability. Sheer stress and horizontal transport rates, however, are minimal during these times.

ICP ANALYSES OF SELECTED WATER SAMPLES

On August 9, 1990, aliquots of approximately 500 ml were taken from each of the eleven regular water samples delivered for routine chemical analysis. Five ml of reagent grade HNO, were added to each aliquot. In addition, a 500 ml sample of water collected several days earlier from the un-named spring in the West Fork of the Black River near the ASARCO minewater pond discharge was also acidified with HNO,. The springwater specimen had been held at room temperature in a closed container for several days and during that time had turned dark brown with considerable accumulated dark precipitate on the bottom and walls of the plastic container. Upon addition of HNO,, the precipitate quickly dissolved and the brown color disappeared. Acidified samples were then taken to the Environmental Trace Substances Research Center (ETSRC) in Columbia, Missouri for Induction-Coupled Argon Plasma (ICP) spectrometric analysis. The results of these analyses are shown in Table 11. The data indicate that those sites consisting of or affected by nearby industrial effluents (#2, #4, #7, #8, and #9) all displayed markedly elevated levels of Fe, K, Na, and Sr, as compared with the other sites. Concentrations of By Co, Li, Mn, Ni, Pb, and Zn were slightly higher, as well, and there were detectable quantities of Cd, Cu, and Mo in affected sites, while samples from the other sites were all below detection limits in these three elements. The un-named springwater sample displayed markedly elevated levels of Ca, Fe, K, Mg, Mn, Na, and Sr.

A second set of acidified aliquots, including a sample from the un-named West Fork spring, was collected on August 24, 1990 and taken for ICP analysis. Acidification of all samples was done within four hours after collection. The results obtained on this group of samples are shown in Table 12. Samples from sites consisting of or affected by nearby minewater discharges (#2, #4, #7, #8, and #9) displayed markedly elevated concentrations of Fe, K, Na, Sr, and Zn. Concentrations of B, Co, Cu, Li, Mn, Mo, Ni, and Pb were also slightly elevated, when compared to the other sites. Once again, the un-named spring in the West Fork displayed remarkably elevated concentrations of Ca, Fe, K, Mg, Mn, Na, and Sr.

On June 27, 1991, a third set of water samples was taken for ICP analysis. (See Table 13.) As in samples taken the previous year, concentrations of K, Na, Sr, and Zn were markedly elevated in samples consisting of or taken near minewater discharges. Concentrations of B, Co, Cu, Fe, K, Li, Mn, Ni, and Pb were also slightly higher when compared with samples from unaffected sites.

ICP analyses of samples taken July 14, 1991 from the un-named spring in West Fork, Welch Spring, Lane Spring, Montauk Springs, the Fletcher minewater discharge, and Love Creek (near Rolla) offer interesting and useful comparisons. (See Table 14.) When these various waters are compared, the West Fork spring displayed markedly elevated concentrations of Ca, Fe, K, Mg, Mn, Na, Sr, and Zn, and slightly higher concentrations of Al, B, Co, Li, Ni, and P. Love Creek also showed elevated concentrations of K, Na, and P, with.slightly higher concentrations of Al, B, Ba, Fe, and Li when compared with most of the springwater samples.

Table 10.

HONTH Jan 10,90 Jan 26/90 Feb, 90 H a r t 90 Apr ,SO Hay 10,90 Jun 6/90 Jun 15/90 Jun 21/90 Jun 29/90 Jul 19/90 Jul 26/90 Auq 3/90 Auq 10,90 Auq 17/90 Sep 14/90 Sep 28/90 Oct,90 .

Nov 20,90 Nov 29/90 Dec, 90 Jan,91 Feb, 91 Har,91 Apr (91 Hay,91 Jun,91 Jul,91 Auq,91 SePI91 Oct,91 Nov ,91 Dec,91

AVERAGE STD. DEV .

STREMI PLOW DATA PWVIDED BY ASARCO ( A . Hil ler)

West Pork CPS 24.40 59.24

High Water High Water High Water High Water

70.76 47.81 41.41 28.70 22.89 23.33 16.80 16.22 28.96 20.55 17.04

NO DATA 21.78

>40 27.62 - >40

>40 39.77 - >40

>40 29.89 - >40 23.33 - 27.47 19.10 - 22.76 16.66 - 24.01 17.32 - 22.27 18.13 - 25.86 18.95 - 28.45 25.00 - >40 32.10 - >40

West Fork HGD 15.77 38.29

nine Pond CFS 2.06 2.75

High Water High Water High Water

2.50 2.25 3.19 2.91 2.67 2.41 2.83 2.81 2.51 3.53 2.33 2.44 2.56 2.61 3.03 2.91 1.28 1.58 1.36 1.54 1.63 1.72 1.46 1.47 1.41 1.42 1.47 1.41

nine Pond HGD AVE DAILY RAINFALL ( in) 1.33 1.78

t-' g (0

N W w I - " . . . . . . . .

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N . . . . . . P N . . . . . . W

w O W w w r p o o o 4 P O 0 0 o r o 3t N C O w 0 o o w 4 N N O W N W o P

0 O O O O W W O O P mCnN m N N m

m O N o m o o

4 N . . P . .P . . .

0 0 0 0 0 w - P O 0 0 0 0 3t N 0 o m P P Ln P O 0 0 W

P m r 0 0 0 O O P Cn Cn m s s w

W w m . . P " . P . P . P . . O C 4 N 4 O I O W C n C 0 0 3t C P 0 0 m o o o w 0 2 z C C n W 0 0 W O W O C 0 N

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w N . IU. C . .

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0 0 P cn O N 0 cn 0 0 0 0 - % Z g P o o o o o e O & N

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;q . . . P ,+ C L cp i % * b b i ~ cocc locu Elb,= @_ o o r o P N L w Ih u w \ w m !s 0 0 0 0 1 C ) O P O C l l W C o o 0 0

ij

N C

N . . P W .W. . . . a W

W O W W O O C 0 a C U O W N

\ D O a e a b = = b k + O O O \ D O P gs=@& a = * o c n N * m a L a rn

w N . P . P O W 0 21 21 0 0 0 0 0 W O W 0

P QI . . W P . . Y . ? . . o O W w C b L w ~ o c u o c o o a C w m w O N 0 W O O 0 0 C 0 cn u

-4 w C

w w m o o o o o o m O W o o N

N N N

P . P . ?'. . . . P . . O P O W 0 W O O $ 0 C N O O l O N o m 0

0 W O

0 0 P O N O W P W O

L.. 1.. I- N W

f IU . F . . IU. W . . F . . . N 0 N r C n o o ~ n 0 C N O b b m o w 0 * 4 w o W O C P O N 0 4 - m o o P W C ~

o o o o w o o o o m m e o .a o o 43

01 0

N C Y . . . . .

P c a o a 0 4 W O O OW 0 0 0 - 0 0

~ ~

0 0 W 4 4 o m cnoo 01 0 0 4 4

* 0 E2 g 01 0 N O O W 0 0 * P 0 0 W O O P W 0 4 Cn e

Table 14. RESULTS OF I@ ANALYSES SAHPLES COLLECTED 14 JULY 1991

7-. . -- -.. ELmWT <#P SPR. .m SPB. ''; WELCH LANE - - -.._ AG

MNTAIJK FLETCHER LOVE CR. Dm LIH .0100

.030 .060 .0200 ,0400

,150 .071 .0200 .037 .025 ,084 ,0005

.0006 ,0400

27.500 32.300 35.400 .3000 .0020 ,0100 .0100

,019 .0020 .010 .I30 ,063 ,0050 .600 2 3.700 .2000

.010 .0100

.031 .002 .0020 16.700 21.900 22.600 .0300 .037 ,064 .035 ,0020

,008 .0050 2.610 33.400 45.200 .O200

.020 ,0100 ,740 ,1000

.050 ,0400 ,0400 ,0400

4.010 3.340 2.860 ,0100 -.. - --. ra-,, ,0400 ,033 '-262 ,067 .0005 -- .0020

.0400

.0030 ,002 .014 .0020

On January 9, 1992 a series of water samples was collected from the following locations for purposes of further comparison and characterization of the un-named spring in the West Fork of the Black River:

a. Recycled process water from a faucet in the mill. This sample is probably representative of water impounded in the main tailings pond.

b. Dripping water collected from the ventilation shaft east of the minewater pond. c. Station #7, minewater pond discharge pipe. d. Station #8, underground pipe from mine. e. Un-named spring in West Fork f. Duplicate sample from un-named spring in West Fork g. Iron-stained spring on bank near discharge channel. h. Iron-stained spring or seepage a t the base of the Southeast Dam. i. Iron-stained seepage from drain field tubes a t base of main tailings dam. j. Station #6, West Fork of Black River a t old Hwy KK. k. Station #lo, West Fork 1% miles downstream 1. Station #11, Mill Creek at confluence with West Fork m. Martin well, north side of river across from ASARCO. n. Elmore spring, % mile downstream from mine.

All samples were analyzed for phosphate, nitrate, nitrite, ammonia, alkalinity, hardness, pH, conductivity, and total dissolved solids. Aliquots of 500 ml were removed, acidified with 5 ml of reagent grade HNO,, and delivered to ETSRC for ICP analysis. Results of these analyses a re summarized in Table 15. There a re many obvious differences between the un-named spring and the water of the main river, the underground minewater, the Martin well water, and the Elmore spring. However, these preliminary data strongly suggest that the underground aquifer that emerges as a spring in the West Fork near the minewater pond discharge also emerges several other places throughout the valley now occupied by the ASARCO mine-mill complex. Similarities and differences among the various samples a re perhaps made more easily apparent by assignment of +'s and -'s to indicate approximate comparative levels of each of the various water quality parameters. This attempt ,

shown in Table 16 for six of the water s a m p l e s . c ~ a n y ilmilarities can be seen in the ICP data for \ ; water samples takenfrom 1) the spring in the river bed itself, 2) the iron-stained spring emerging a t \

several places on the south bank of the river near the industrial discharge channel, 3) the water I trickling from the base of the southeast dam, as well a s 4) the iron-rich water trickling from the drain

P Ni, o andZn-in-thi3dralntiela samples a t the base of the main tailings dam and the southeast dam, L -

strong correlations are indicated in relative concentrations of Ca, Fe, K, Mg, Mn, Na, P, Sr, as well

/ f'eld a t the base of the main tailings dam. ough-the data indicate minor differences, i.e.

a s alkalinity, hardness, and conductivity. There a re several distinct differences between the "chemical fingerprint" of the springwater and the mill process water and, presumably, the water of the main tailings impoundment. Specifically, the recycled mill process water indicated significantly greater concentrations of Cu, K, Ni, Sr, Zn, nitrate, nitrite, and ammonia than the springwater. The mill process water also showed significantly lower concentrations of Fe, Mn, P, and lower alkalinity than the springwater. When compared with the drain field seepage from the base of the main tailings dam, the mill process water (taken from the main body of the tailings lagoon) showed elevated levels of Cu, Zn, nitrate and nitrite, and distinctly lower concentrations of Ca, Co, Fe, Mg, Mn, Ni, P, Sr, ammonia, and lower alkalinity, hardness and conductivity.

Local residents and long-time employees of the mine report that the valley on the south side of the river was quite marshy or boggy before construction began. Experimental drill holes on the north side of the river, especially in the dry stream bed near the Martin farm, sometimes tapped into impressive aquifers, causing underground water to gush out of the holes. These holes and the resulting artesian flow were subsequently grouted and sealed. Many recall the tremendous aquifer or spring encountered near the surface when the shaft was dug fo r the ventilation system near the hill, east of

W N I-

W

P . " . . . . . W . . PO . . . W N N W I - m O 0 m O O I - 0 0 0 4 0 I- 0

s 4 w 0 u W O W I - 0 W C . O P W m 0

0 0 0 0 W 0 w 0 0 W W P 0 N N P m o o

8 0 w 0 s

N N W

P , P . . IU. W . . . . " . . . N N N C . C . O O ~ O N W O 0 0 0 3 o w 0

z g W O - N O N 0 0 - m 0 0 NNCll

z W 2 g 0 O O O + O O O O N 4 W O

v m W O O m

A

4 I- . . IUP

N P . I - W W I - W O W m w W 4 O m O o N W W N O O C n O C n

r -03 vj

0 ,w1m . ?F, . v . . . . a u

o O N ;3 o L b k I o w - o o w N m

O W N m 0 z s =:8 S818 N w 0 w

4 - 2 m o

4 I- cn I " . 0 N . . m

N Eu 0 " C b "' " W W

0 I- 4 I-

0 I- m

4 o g S 8 8 Z E 8 w o m o

m 4 0 E

) WN'?',. t". . . N m p . m m o o 0 m N m 4 W O O P N O O 4 O ~ N O \ D W O L

. . . A 4

C.W. clW00CnP m N W m P W O w 0

I - N m N O W m N O m

the present minewater pond. Huge amounts of concrete now effectively seal the ventilation shaft. There seems to be little doubt that this underground aquifer, emerging at numerous places in the valley, existed prior to construction of the mine-mill complex. It is important to point out that the main tailings lagoon was designed and constructed with an impervious clay liner to achieve zero discharge and allow complete recycling of mill process waters. Previous studies conducted by ASARCO personnel utilizing fluorescein dye placed in the main tailings lagoon showed no apparent seepage of mill effluents from the main tailings lagoon or mill pond into the river or regional aquifers - - (Ed Smith-nal c o m m u n i c a t i o ~ ~ ~ h o u g h the exact source of the un-named spring and its ,

\ f contributing aquifer remains uncertain, there is no evidence in the current data to suggest that the mill i water or tailings a re escaping into the river. --..- ---_,,-,.--~ - -

'h -

,- 1

-..-- - - .-- ---- -1

COMPARISON O F SPRINGS AND SEEPAGE WATER SAMPLES O F JANUARY 9,1992

Table 16.

Southeast Main Dam Tailings Dam

+ + + + + + + +

Criterion Mill Water W.F. Spring Spring on I Bank

Elevated Ca I + + 1 + +

Elevated Cu I - I - Elevated Co -

NO,

NO2

N H4

ALK

HARD

COND

- - -

+ + +

+ + + + + +

+ + + + + + + + +

CONCLUSIONS:

K T h e b 6 G n mat that develovs on the bottom rocks of the West Fork of the Black River near the

Moueeotia, with small amounts of ~ e o c l o n i u m , which seem to persist in the discharge channel and in the vicinity of the confluence-with West Fork.

die, are consumed, or decompose, the released nutrients may be transported downstream, encouraging development of downstream algal communities. Because of horizontal transport and increased nutrient load in the river at some downstream sites, the severity of algal blooms may be affected by contributions from upstream sites.

3. The drainage basin of the West Fork of the Black River down to the confluence with Mill Creek is approximately 48,000 acres. Within that drainage basin there is a number of houses and farms, with cattle horses, goats and animals. Runoff from this vast forested area may be expected to nutrient load to the West Fork and its tributaries.

4. Growth of algae is inevitable in any non-toxic stream or impoundment where there a re dissolved nutrients, even in small quantities. Nitrogen and phosphorus are probably the principal limiting nutrients in freshwater environments. Addition of significant quantities of these nutrients to a river or impoundment, either by natural runoff, underground seepage, or anthropogenic sources, can be expected to result in an increase in the productivity of the aquatic environment.

5. The ASARCO West Fork minewater discharge of approximately 1-2 mgd, consisting of excess underground water pumped to the surface to permit underground operations, contributes an - appreciable amount of nutrients to the West Fork of the Bla . Nitrogen, In the form %f nitrates (1.88 f .67 ppm N), nitrites (0.07 m~ ppm N onia (0.661 f .29 ppm N), amounting to approximately 37.6 pounds (as N), is added each day to the West Fork by this single source. In addition, with a mean phosphate content of 0.024 k .02 ppm (as P), the mine water adds approximately 0.35 pounds ot phosphorus to the river each day. These values,

L

, however, are not too dissimilar from the nutrient content of many regional springs, such as . 7 r Montauk, Alley, Lane, Welch, or Meramec. Phosphate concentrations a re not significantly

4

;. . , L -,

6. The minewater discharge is much like having a sizeible spring bringing underground water to the surface. Like most n a t u r a r 3 3 r i n i i h e underground waters contain sufficient nutrients to encourage the growth of photosynthetic organisms in the vicinity of emergence.

7. Near the point of discharge of the ASARCO West Fork minewater, a separate spring emerges within the river bed and at several locations along the south bank of the river. Preliminary

data indicate it may also emerge at other places throughout the valley. The un-named spring has markedly elevated levels of Ca, Fe, K, Mg, Mn, Na, and Sr. Though usually low in nitrate- N it often displayed somewhat elevated levels of ammonia-N, phosphate, and extraordinary hardness. Judging from its peculiar chemical and physical characteristics, the springwater is quite unlike other regional or nearby springs, and distinctly different from the main river water, the underground minewater, or recycled mill process water.

8. The marked discoloration of rocks and algae, and the abrupt change in appearance of dominant algal forms near the minewater discharge into West Fork is largely due to the influence of the un-named springs which emerge in the river bed and along the bank. The darkly-stained rocks in the vicinity of these springs have been found to be coated with a thin layer of manganic and ferric materials which quickly precipitate out when the underground waters are exposed to surface air. According to reports in the literature, manganese and cooler temperatures a s the underground waters mix with the river, may be partly responsible for the abrupt change in the appearance and structure of the algal community. Manganese and cooler temperatures reportedly encourage the development of diatom communities, rather than the green, filamentous algae typically found in greater abundance at upstream sites. Blackened rocks, with similar surface coats of manganese and other co-precipitated metals, are commonly observed in several mine or mine-mill industrial discharge channels. Exposure of underground manganiferous rocks to percolating waters encourages solubilization of manganese and associated metals, found in many subsurface rocks. Blackened rocks are commonly observed on many hillsides, and along riverbeds and river banks throughout southern Missouri. Localized manganese deposits, often accompanying iron deposits, a re quite common throughout south central Missouri. It is difficult to discern whether blackened rocks and algae at this point in the West Fork of the Black River a re caused by manganese mobilized by industrial activities or by naturally percolating groundwaters in manganiferous deposits.

9. In comparison with reported algal blooms in the literature and some observed in other regional -. . streams during the course of this study, the West Fork blooms must be considered moderate

vr ' in intensity and nuisance impact, and limited in duration. Algal growth to reach to late summer months during periods of til:ymDmrrerature

most of the cold months and periods of high river flow, a re prevented.

R - bV- J 10. The moderate intensity of algal blooms in the West Fork of the Black River is consistent with

6" opinions expressed in the literature that serious algal blooms rarely occur where nitrate-N is less than 0.3 ppm and total N is less than approximately 0.6 ppm. Nitrate concentrations in the main river channel a re generally below these recognized levels. Though minewater and many

. .. springs typically contain mote nitrate-nitrogen than 0.3 ppm, dilution within the larger river, and flowing water conditions often prevent accumulation of nuisance attached algae. Perhaps of even greater importance in avoiding serious algal blooms, the observed phosphate-P concentrations within the minewater and the main river a re generally well below the critical 0.1 ppm level recognized a s conducive to algal blooms.

11. The Grand Daddy Hole acts a s a natural trap for nutrients, debris, leaf litter, and algal scum. Its deeper pools act a s zones of decomposition and recycling of nutrients, while the shallower areas within the swimming hole and the riffle zones nearby allow greater photosynthetic growth. Because of its location near a sharp bend in the river, the slowed current and greater depth, this particular hole will continue to enjoy the benefits of horizontal transport and increased sedimentation, especially during periods of low flow.

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ACKNOWLEDGMENTS

Technical assistance in chemical analyses provided throughout the course of this study by Jennifer Shelley, undergraduate Life Sciences laboratory assistant, is gratefully acknowledged. Appreciation is also expressed to UMR undergraduate Robert Shelley, for occasional assistance with numerous routine chemical analyses and to Robert Johnston, University of Manitoba, for his guidance in statistical analysis of the data.

APPENDIX A

NITRATE-NITROGEN CONCENTRATIONS

ELEVEN REGULAR SITES

NITRATE-N

West Fork North low Water Xing Bills Creek @ low Water Xing Bills Creek @ Tailings Pile Brushy Creek Hine Discharge West Fork Below Bills Creek West Fork @ Old HWY West Fork Hine Pond Discharge Hine Pipe West Fork - Grand Daddy Hole West Fork - 1.5 Hiles Downstream Hill Branch

Nltrate Concentration (mgWL) 0 0 0 0 d d

NITRATE

0 2 0 40 6 0 8 0 HEEK

Nitrate Concentration (mg-WL)

NITRATE

Nitrate Concentratlon (mgWL)

NITRATE

NITRATE

Nitrate Concentration (mgNL)

NITRATE

Nitrate Concentration 0 0 0 0

NITRATE

Nitrate Concentration (mgWL)

A-18 NITRATE

Nitrate Concentration (rngNL)

NITRATE

Nitrate Concentration (mg-NIL) 0 d d

0 0

R 5 S 0 g 0 g 0 C a

A-22

NITRATE

40 WEEK

Nitrate Concentration (mgWL)

A-24 NITRATE

40 WEEK

Nitrate Concentration (mpNIL) 0 0 d d

NITRATE

APPENDIX B

N I T R I T E - N I T R O G E N CONCENTRATIONS

ELEVEN REGULAR SITES

NITRITE-N

West Fork North bw Water Xing Bills Creek @ bw Water Xing Bills Creek @ Tailings Pile Brushy Creek Hine Discharge West Fork Below Bills Creek West Fork @ Old HWY West Fork Hine Pond Discharge Hine Pipe West Fork - Grand Daddy Hole West Fork - 1.5 niles Downstream Hill Branch

o o o k l o o o o o o o a- 0 0 0 k l m 0 0 0 0 0 0 0 0 k l 0 Q , 0 0 0 0 0 0 0

-. . . . . . . . . . . . \ 0 0 0 w 0 0 0 0 0 0 0 a o o o w m o o o o o o o k l k l O w W k l 0 m 0 0 0

o o o w w o o o o o o a- o o o m ~ o o o o o o t- w m ~ m a ~ ~ a m ~ w

. . . . . . . . . . . . 0 0 0 w 0 0 0 0 0 0 0 Lo O O O W P O O O O O O t- O P V I w w m 0 m 0 0 0

Nitrite Concentration (mg-NIL)

N I T R I T E

Nitrite Concentration (mg-N/L)

N I T R I T E

n nnn Y u. UUU

0 2 0 6 0 80

Nitrite Concentratkn (mg-NIL)

N I T R I T E

Nitrite Concentration (mg-N/L)

N I T R I T E

Nltrite Concentration (mg-NIL)

E l 4 N I T R I T E

0 20 40 6 0 80 HEEK

Nitrite Concentration (mq-NIL)

8 0

8 d

8 d

VI 0 VI

N I T R I T E

WEEK

Nitrite Concentration (mg-NIL)

8 0 A

P A

VI 0 VI R 0

0 0 0 0

40 HEEK

Nitrite Concentration (mgWL)

N I T R I T E

40 60 HEEK

Nitrite Concentration (mg-N/L)

B-22 N I T R I T E

0.000 e n CL CI m V

0 V U U U

20 V

40 60 8 0 UEEK

Nitrite Concentration (mg-WL)

N I T R I T E

Nitrite Concentration (mg-NIL)

8 P 0

0 0 8 d 8 d

0 ul 0 ul

N I T R I T E

* 0 20 40 60 80

U

HEEK

APPENDIX C

AMMONIA-NITROGEN CONCENTRATIONS

ELEVEN REGULAR SITES

West Fork North L o w Water Xing Bills Creek @ L o w Water Xing Bills Creek @ Tailings Pile Brushy Creek Mine Discharge West Fork Below Bills Creek West Fork @ Old HWY West Fork Mine Pond Discharge Hine Pipe West Fork - Grand Dadddy Hole West Fork - 1.5 Miles Downstream Hill Branch

- 10 CSR 20-7-NATURAL RESOURCES -- Division 20-Clan W a t a ~ 4 m m i r t i o n ~

Chronic Criteria for Total Ammorri.: General Wum-Water Fmhery (mg/l) 7 Tem~. DH

Acute Criteria for Total Ammonk General Wum-Water Fmhery (mgll)

Ammonia Concentration 0 ' 0 0 0

AMMONIA C- 7

0

0 U U

20 U

40 60 8 0 WEEK

Ammonia Concentration

8 P -. 0 0 E z

0 0 0 0 0

C-9 AMMONIA

.500

Ammonia Conwntratbn (mg-N/L)

AMMONIA

WEEK

Ammonla Concentration (mg-NIL)

AMMONIA C-13

40 HEEK

Ammonia Concentration (mg-N/L) 8 . 0 -. R 0 0 0 0

X 0

0 0 0 0 0

AMMONIA

U

0 r)

0

a3 r) P.

0 U

20 40 6 0 SO HEEK

Ammonia Concentration

AMMONIA

0 2 0 40 60 8 0 -

WEEK

Ammonia Concentration (mg-NIL)

A M M O N I A

Ammonia Concentration (mg-N/L)

AMMONIA

40 WEEK

Ammonia Concentration (mg-NIL) P & R P

0 0 0 0 0 0 0

E 0

AMMONIA

40 WEEK

Ammonla Concentration

Ammonia Concentration

AMMONIA

0 nnn

40 WEEK

APPENDIX D

PHOSPHATE-P CONCENTRATIONS

ELEVEN REGULAR SITES

PHOSPHATE-P

West Fork North low Water Xing Bills Creek @ low Water Xing Bills Creek @ Tailings Pile Brushy Creek Mine Discharge West Fork Below Bills Creek West Fork @ Old HWY West Fork Mine Pond Discharge Mine Pipe West Fork - Grand Daddy Hole West Fork - 1.5 Mile Downstream Mill Branch

- - I-.

- . . . . . . . . . . . - 0 0 0 0 0 0 0 0 0 0 0 P O O N O O O O O O O s U O L n W U O w O W 0 0

Phosphate Concentration (mg-PlL)

8 8 8 8 0 P 0 A

0 A

0 N P 0, 00 0 0 0 0 0 0 0

N 0

PHOSPHATE D-6

Phosphate Concentration (mg-P/L)

PHOSPHATE

Phosphate Concentration (mg-PIL)

PHOSPHATE

Phosphate Concentration (mg-PIL)

Phosphate Concentration (mg-P/L)

PHOSPHATE

40 HEEK

Phosphate Concentration (mg-PIL)

D-24 PHOSPHATE

PHOSPHATE D-26

0

Phosphate Concentration (mg-P/L)

8 0 8 h) E 8 rn f o d 0 d

0 0 0 0 0 0 0

APPENDIX E

ANCILLARY WATER QUALITY DATA

- 8

ELEVEN REGULAR S I T E S

7 SITE DATE TDS uS/cm ALK HARD pil 1 03/06/91 149 298 154 162 1 04/05/91 130 261 132 138 1 05/09/91 133 265 132 140 7.72 1 06/06/91 153 305 156 160 7.53 1 06/12/91 155 309 163 164 8.29 1 06/20/91 165 330 176 176 7.64 1 06/27/91 167 334 180 180 7.65 1 07/11/91 169 338 182 182 7.52 1 07/18/91 173 346 184 192 7.56 1 07/25/91 178 355 7.49 1 08/01/91 179 358 194 196 7.43 1 08/15/91 181 361 192 194 7.53 1 08/22/91 182 365 7.64 1 08/29/91 183 366 7.66

164.07 327.93 167.73 171.27 17.66 35.35 22.06 20.30

-'I SITE DATE TDS uS/cm MX MRD Pa 4 05/09/91 226 451 150 202 8.08 4 06/06/91 254 508 164 220 7.87 4 06/12/91 254 508 166 228 8.56 4 06/20/91 260 520 168 226 8.13 4 06/27/91 264 528 170 230 7.94 4 07/11/91 272 544 172 236 7.74 4 07/18/91 278 556 174 240 7.88 4 07/25/91 281 561 7.90 4 08/01/91 280 559 178 246 7.74 4 08/15/91 289 577 178 244 7.80 4 08/22/91 289 578 7.97 4 08/29/91 287 57 5 7.98 .

270.07 539.86 169.36 232.55 18.13 36.28 8.46 15.29

SITE DATE TDS US/CB ALK HARrl pH 7 06/12/91 218 435 164 182 8.24 7 06/20/91 221 442 166 186 7.80 7 06/27/91 223 446 164 190 7.89 7 07/11/91 228 4 55 166 194 7.86 7 07/18/91 233 466 162 200 8.02 7 07/25/91 231 461 7.89 7 08/01/91 230 4 59 164 194 7.78 7 08/15/91 234 467 168 190 7.62 7 08/22/91 231 463 7.76 7 08/29/91 228 4 57 7.93

226.07 452 164 189 5.46 10.78 2.19 6.24

SITE DXJE TDS uS/m AM HARD PH 10 06/27/91 175 351 164 178 7.73 10 07/11/91 179 358 166 184 7.34 10 07/18/91 185 369 166 184 7.72 10 07/25/91 187 374 7.68 10 08/01/91 157 314 168 172 7.76 10 08/15/91 197 394 174 194 7.52 10 08/22/91 175 349 7.50 10 08/29/91 177 354 7.74

170.86 341.64 156.55 170.55 14.97 29.86 13.30 15.05