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Water Quality as Related to Water Pollution in California In contrast to states that base their

i

pollution-control programs on fixed effluent standards, maximum degree of treatment, or classification of streams, California legislation embodies the principle of case-by-case determination of whether a pollution exists or threatens in any area. To administer such a program, complete information must be available on quality-quantity characteristics of surface and underground water, present and future beneficial uses of water, and long-range plans and policies. A statewide sampling program on ground-water basins is still largely in the planning stage, but in addition to intensive studies on surface waters in some areas, a monthly sampling program has been under way since 1951 at approximately 130 stations on over 50 streams and lakes.

VINTON W. BACON California State Water Pollution Control Board, Sacramento, c a l v .

GEORGE B. GLEASON California State Division of Water Resources, Sacram.ento, Calif.

N E W and entirely different concept was embodied in the California water-pollution control program created by the 1949 Legislature (IO). It was designed to provide the means for establishing an equitable and economic balance among the many beneficial uses of water by application of the principle of case-bycase determination as t o whether or not a condition of pollution threatens or exists. This principle provides that each pollution problem be analyzed individually to determine its effect upon present and future beneficial uses of water in accordance with long-range plans and policies which, by statute, must be formulated by the water pollution control boards. Furthermore, these plans and policies in all cases must be coordinated with the State Water Plan as adopted by the California Legislature. I n contrast, many states have based their water-pollution control programs on k e d effluent standards, minimum degree of waste treatment, or classification of streams. These programs have the advantage of simplicity and ease of administration, for they are well defined and equitable among communities and industries, Their primary disadvantage lies in their uneconomic use in some cmes of the assimilative power of the receiving waters or disposal areas. Of necessity the case-by-case approach used in California precludes a broad-brush treatment on a statewide or even regional basis, and it rules out rigid stream standards and the arbitrary zoning of streams or underground basins. I n effect, it depends on astute judgment by members of the water pollution control boards. Such judgment must>be founded on a complete knowledge of the facts of each case, which include: (1) quantity and strength of wastes, (2) beneficial uses of water to be maintained and protected, (3) water-quality requirements for these beneficial uses, and (4) quality of receiving waters in their natural, unpolluted state. Beneficial uses of water may include domestic water supply, agriculture, recreation, wildlife propagation, industry, power development, navigation, esthetic enjoyment, and waste disposal. A41thoughcharacteristics of wastes, beneficial uses of water, and w-ater-quality requirements are equally important considerations

December 1953

I. W . WALLING Quality of Water Branch, U . S . Geological Survey, Sacramento, Caltf.

in pollution problems, this paper is confined to a discussion of the program for obtaining basic data on ground water, surface water, and pollution effects on water quality. GEOCHEMISTRY

Because of the wide variation in geologic complex, climate, and other variables, it is difficult to generalize on the geochemistry of the natural waters of California. Generally, rainfall governs the concentration of soluble minerals in the water through the effects of dilution, and the kind and proportion of mineral solubles in the water are governed by the types of minerals composing the rock materials and soils with which the water comes in contact. Figure 1shows the natural geologic provinces and Figure 2 shows the average annual rainfall distribution in the state. Surface and ground waters draining from the north coastal area (corresponding on Figure 1 to the Klamath Mountains and the northerly one half of the coast ranges), the eastern side of the Central Valley area (corresponding roughly t o that area designated as Sierra Nevada), and the western segment of the coast ranges are of especially good quality (see Figure 3 also). Analyses show that the surface and underground waters in these three broad areas possess very low concentration of soluble minerals and hardness, low per cent sodium, and relatively small amounts of boron. These waters are of the bicarbonate type and calcium is the predominant base constituent. As will be noted on Figures 1 and 2, they are produced in areas underlain by igneous rocks and in areas having the greatest amount of rainfall. Surface runoff from these three areas makes up approximately 90% of the total for the entire state, and the north coastal area alone accounts for 40% of the total. In contrast, relatively large amounts of mineral impurities are contained in waters which occur in areas characterized by one or more of the following factors: low precipitation, interior drainage, poorly consolidated deposits of marine origin, and fault zones through which mineralized juvenile and recirculating meteoric waters are introduced into drainage and ground-water basins. Waters of comparatively high salinity occur in the west side of the

INDUSTRIAL AND ENGINEERING CHEMISTRY

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rather high dissolved solids concentration can be correlated with the occurrence of fault zones. These waters not only show high concentrations of dissolved solids, but also have a high boron content, a constituent which may be indicative of water from deep-seated sources. SURFACE WATER

One of the first acts of the State JVatei Pollution Control Board after its creation in 1949 was t o initiate a statewide sampling and analytical program on the surface streams and lakes, in order to obtain data on quantity and quality of the unpolluted water resources. By confining sampling to unpolluted waters, data obtained would serve as a “baseline” to measure changes caused by natural or man-made pollution. -4t the beginning of the program, samples were collected a t approximately 60 stations on 30 major streams and two lakes. As of March 1953, the program had been expanded to include 148 stations on 88 major streams and lakes. In most instances, the sampling stations are located a t or near streamgaging stations, as concurrent discharge measurements are necessary to correlate the quantity of dissolved solids or constituents with stream flow, Monthly samples are collected at each of the stations and are analyzed for physical, chemical, bacteriological, and radiological characteristics. The field men have been trained in the technique of collecting samples for these different determinations. During collection of samples, field Figure 1. Natural Geologic Provinces of California measurements are made for temperature, dissolved oxygen, pH, stream-gage reading, and Central Valley from the Cache Creek drainage area in the Sacraunusual color or turbidity. One sample collected from each station is analyzed for chemimento Valley south to the Tehachapi area in the southern part of cal constituents by the U. S. Geological Survey or the State DiviSan Joaquin Valley (corresponding roughly t o the area immedision of Water Resources. During IO months of the year, a “parately west of the axis of Great Valley synclineon Figure 1). ii-ative tial” analysis is made, which includes determination of electrical waters of inferior quality also occur in basins on the west slope of conductivity, chlorides, bicarbonates, hardness, turbidity, color, the Diablo Range that separates the central coastal and Central and coliform count. On two of the monthly samples-during the Valley areas, in the Cuyama and Santa Maria River basins in the month of high flovi and during the month of low flow-complete central coastal area, in the Ventura River basin, and in Piru and analyses are made which include, in addition t o the above: calSespe Creeks in the south coastal area. Water of very poor cium, magnesium, sodium, potassium, iron, aluminum, inangaquality also occurs locally in the Modoc Plateau and throughout nese, zinc, copper, lead, arsenic, sulfate, nitrate, fluoride, hesavat h e Lahontan (basin ranges and Mojave Desert) and Colorado lent chromium, boron, silica, and radioactivity. Desert basins, where soluble minerals frequently include sigBacterial testing is done by the State Department of Public nificant amounts of boron. Other constituents, including trace eleHealth in its laboratories. Presumptive and confirmed tests for ments such as fluoride, may also be present in large quantities. the coliform group are made on duplicate samples collected Large bodies of poor quality connate water also occur a t relamonthly from each station. All bacterial work is done in accordtively great depth in most of the coastal ground-water valleys, ance with the procedures of the American Public Health h s o basins, and under alniost the entire area of the Great Central ciation (1) and results are reported in most probable number Valley. (MPX). Table I compares the mineral characteristics of two suiface streams in areas having widely different climatic conditions and geologic complexes. The water in the American River reflects T i B L E I. MINER.4L CHARACTERISTICS O F SURFACE S T R E A V S conditions of abundant precipitation and runoff from areas underINFLUENCED BY CLIMATIC AND GEOLOGIC CONDITIOXS laid largely by igneous rock materials. Conversely, the qualitv Concentrations of Minerat Constituentsa, of the water in the Cuyama River is evidence of comparatively P.P.I\l./%b $ow rainfall and runoff from areas composed of poorly consoliCations Anions Stream Ca Mg h’a HCOI C1 Son Total dated sandstones and shale into which mineralized juvenile and 3 1 2 18 1 2 27 American River near recirculating meteoric waters may have entered through fault Sacramento 25 9 16 43 2 5 100 zones. There is a wide variation in both the concentration and Ijo E 120 300 2 590 1300 Cuyama River near composition of soluble mineral in the waters of the two streams. Santa Maria 21 16 13 13 5 32 100 The source of waters with unusually high concentrations of Spot samples collected during spring runoff, dissolved constituents or with unusual constituents can someb Per cent of total reacting values (combining power of chemical substances in solution as compared t o reaction capacity of 1.008 p.p.m. of hytimes be traced to a region in the proximity of geological faults. drogen). This is true in the headwaters of the Santa Ana River, where

2658

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 45, No. 12

Industrial Process Water During 1952-53 three samples representing low flow, high flow, and intermediate flow a t each station will be analyzed for radioactivity. Determinations include gross alpha and gross beta-gamma, and a distinction is being made between the radioactivity of the total dissolved solids and the total particulate solids. This work is being done by the Radiological Services laboratory of the State Office of Civil Defense. I n addition t o the state-financed monthly sampling program, six daily sampling stations are being operated in the Central Valley, being financed by federal funds as a part of the nationwide “Irrigation Network Stations” program. Furthermore, many large municipal water departments, water companies, and irrigation districts routinely collect and analyge samples, which adds to the background of chemical and physical data being accumulated. Plans are being made to include biological sampling at a limited number of stations in the future. A generalization of the quality of native fresh surface waters in California appears on Figure 3. As previously explained, water of low mineral content is found in the north coastal area, the eastern side of the Central Valley, and the western segment of the coast range mountains. Water of low to moderate mineral con-

tent is also found in the south coastal area. I n the remainder of the state, the waters are classed generally as moderate to high in mineral content. Figure 4 shows the wide variation in chemical characteristics of surface waters to be found in the state. The seven rivers and sampling locations depicted (Colorado River at Parker Dam, Salinas River a t Spreckels, San Gabriel River at Whittier Karrows, San Luis Rey River a t Pala, Russian River at Guerneville, Klamath River a t Copco, and Sacramento River a t Knights Landing) were selected from the samples taken as a part of the statewide monthly sampling program during May 1952. The analyses represent a single sample only from each of these sources a t that particular time.

GROUND WATER Approximately half the water used in California is pumped from ground water. This pumpage totals over 10,000,000acre-feet per year. About 275 ground-water basins which are separated one from the other by more or less distinct physical boundariesmountains, hills, fault zones, hydrologic divides, etc.-have been identified by the Division of Water Resources and other interested agencies. The fact that this large, widely distributed supply is relatively immune from enemy attack adds to the importance of its protection from pollution. I n Division 7 of the Water Code of the state of California, which provides for the establishment of the Water Pollution Control Boards and sets forth their r e s p o n s i b i 1 i t i e s , “pollution” is defined as “an impairment of the waters of the state by sewage or industrial waste to a degree which does not create an actual hazard to the public health but which does adversely and unreasonably affect such waters for domestic, industrial, agricultural, navigational, recreational, or other beneficial use.” Section 229, which was added to Division 1 of the Water Code as a companion measure to Division 7, provides that the Department of Public Works, acting through the State Engineer ‘I shall investigate conditions of quality of all waters within the state, including saline waters, coastal and inland, as related t o all sources of pollution of whatever nature and shall report thereon to the Legislature and t o the Regional Water Pollution Control Board annually, and may recommend any steps which might be taken t o improve or protect the quality of such waters.” This section broadens the definition of pollution, in so far as those investigations and recommendations are concerned, toinclude degradation resulting from sewage and industrial wastes, and Geographical Distribution of Precipitation in California that from natural sources.

...

Figure 2.

December 1953

INDUSTRIAL AND ENGINEERING CHEMISTRY

2659

dizing organic matter present in most soils provides more carbon dioxide for solut,ion. The carbon dioxide in solution reacts with soil minerals t,o form soluble bicarbonate salts. Readily soluble minerals present in many rocks and soils go into solution directly. Both the concentration and chemical charact.er of ground waters may be altered greatly by chemical r e a c t i o n s with mineral or organic matter of the containing deposit,s. Principal among these are base exchange reactions (natural softening or hardening) and sulfate reduction. Evaporation of ground waters near land surface and transpirat,ion by plants resulk in concentration of salts and in precipitation of less soluble s a l t s when s a t u r a t i o n is reached. Thus, both concentration and relative quant,ities of mineral matter in solution may change significantly as the result of reaction within the ground-water body. With cultural development on overlying lands, both character and concentration are further modified by contributions from percolating irrigat,ion water which carries down some or the fertilizer constituent,a and from cesspool seepage or sewerage system effluent discharged on the land. So far as is known, nothing can be done t o limit t.he effects of irrigation return, and in many 1 areas the elimination of sewage Figure 3. Quality of Native Fresh Surface W-ater in California return is not feasible. Therefore, from t,he standpoint of oollution control, it, is the DresTo date a sampling and study program of ground water on a ent quality of the water unaffected by controllable pollutants statexide basis is largely in the planning stage. The activities of that is significant rather than its original or “natural” quality. available manpower have been concentrated in more restricted The quality required to meet the demand5 of the various beneareas \There problems have arisen and been recognized. However, as shown on Figure 5 ) a considerable part of the more in- ___ tensively utilized lands of the state has been or is being covered in these special investigations, in the course of which several Io thousand samples have been collected and analyzed. Ground water analyzed to date ranges from a calcium bicarbonate h-pe water of excellent quality for all common uses. to water excessively high in sodium, chloride, sulfate, boron, and other constituents which render the water unsuitable foi one or more of the diverse uses to which it might otherwise be put. The chemical character and conceuti ation of ground water are governed bv the quality of water entering the ground-water body 54 and by chemical changes which occur as the water moves through the earth With the evception of water moving inland from the ocean and juvenile waters from deep within the earth, all ground water is derived directly or indirectly from rainfall Even as rain, natural water contains appreciable quantities of carbon dioxide in solution and small quantities of mineral matter Figure 4. Variation in Chemical Character of Native dissolved from dust particles. When the rain enters the soil, oxiFresh Surface Water i n California

-

*:-

2

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INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 45, No. 12

-Industrial

Process Water

TABLE 11. ANALYSES OF TYPICAL GROUND WATERUNAFFECTED BY CONTROLLABLE POLLUTION NO.

M O L

Conductance, EC X 106 a t 25' C.

1

General Location At Crescent City

2

B t Kirkwood

372

3

Madeline Plains

542

4

Near Sebas topol

420

5

A t Dixon

6

Sutter-Yuba

882

At Stockton

305

A t Santa Claxa

481

.

-

-

-

Near Mendota

12

.4t Fresno

380

13

Near Strathmore

528

14

Cbuoka Walla Valley

15

Near Bakersfield

16

A t Oxnard

17

San Gabriel Valley

367

18

iiear Santa Ana

558

19

Near San Bernardino

227

20

Lucerne Valley

889

21

Landfair Valley

337

22

Fenner Valley

402

23

Twentynine Palms

936

24

.4t C oac hella

304

25

East Salton Sea Basin

26

Ogilby Valley

-

- - 0.02

..

-

1.07

-

-

_ . _ _

-

6320

16.22

702

-

1100

876

~

--

2890

3560

~

-

559

11

---

-

7

At Salinas

+

-

-- --

544

At Plrasanton

+

--

103

539 area

Mineral Constituents, Equivalents per Million Composition, % of Total Cations or Total Anions Cations Anions Boron, Ca M g Na K HCOa COS 804 C1 N o s P.P.M. 0.04 0.27 0.05 0.00 0.24 0.48 0.31 4 26 4 30 24 46 66 0.81 1.45 1.65 2.80 -0.27 _ _ 0.42 _ _ 0 . 2 9 0.01 20 74 6 12, 8 38 42 1 . 3 3 0.46 0.04 0.03 3.97 1 . 7 0 2.14 1.78 23 8 1 68 30 38 32 0.20 0.51 0.90 --Tr 1.80 2 2 1.50 1 2 __ __ 42 12 20 68 34 24 0.38 0.50 0.39 5.21 1.55 3 2 1.43 6 0 10 84 26 50 24 0.03 _ 1 . 4_ 3 0 ._ 00 1.67 3.86 1.59 _ _ -2.05 __ _ ~ 0 27 0 31 39 73 30 5 5 _1.35 1.96 0.60 4.65 1.94 0.34 3.21 -1 ._ 16 14 22 48 46 34 20 0.27 0.56 .. 2.36 1 . 2 0 0.90 1 2 _ _ _ _ -0.06 17 2 73 37 28 34 8 0.81 0.42 0.04 0.18 3.95 1.17 2.84 -~ 76 le 8 0 56 20 24 1.97 0.56 2.17 0.0j 0.04 1 . 8_ 5 -1 . 6 4 2 3 _ -~ 50 10 40 0 34 30 36 22.69 5.02 0.1F, 2 . 4 3.64 4.22 s .21 23.65 __ __ 10 16 2 12 14 72 74 2.77 0.13 1.43 1 . 2 5 1.15 0 . 4 5 0 . 50 0 - _ _ 72 33 30 4 10 14 37 0.80 0 2 3.54 2.79 0.09 0.73 1 . 5 8 __ 15 19 14 30 66 3 53 1.33 44.60 0.68 - 7.00 ~65.18_ 0.06 _ 0 . 9 72 1 11 88 0 26 2 3.49 2.40 4.39 O 0.17 2.60 G 45 24 56 32 31 12 0 4.69 4.80 5.78 1.61 0.2 4.84 7.48 40 40 40 20 48 12 0 2.20 1 . 3 1 0.65 3.38 -0.21 _ _ 0 . 2 0 0.14 0.01 53 31 16 86 5 6 4 1.74 3.10 1.06 ,, 1.04 0.90 3.90 53 18 66 18 15 1 29 1 . 4 0 0.57 0.52 -0.21 _ _ 0 . 1 4 0.03 0.12 21 84 9 6 1 56 23 2.50 4.72 3.53 3 . 5 4 0 2 0.03 2.59 6.49, 22 22 E6 40 80 0 30 2.08 0 2 1.34 2 2 0.46 0 . 5 5 0.14 0.00 53 13 71 34 12 14 8 1 . 9 6 0.23 5.14 1.58 0.58 1.06 0.11 0.00 _.52 6 42 55 14 28 3 4 0 _0.25 6.12 1.86 0.26 7.91 1.60 -1 ._ . 15 3 82 0 64 19 17 1 . 3 9 0.38 1.41 0.31 , . 0.02 1.33 44 12 44 78 lo 12

-

_ .

1.81

-

-

-- -- -

-

--

2.00

-

_ .

-

-

-

0.88 0.04 2 4.19 38

0

2.38 21

36.18 98 4.57 41

-

0 - - 0.07

-

-

-

-

'

0.15

__

-

2.42

9 28 __

26 2.88 25

-

0.09 ~-

---

-

_

I

-- - -..

10.57 15.70 0 2 30 44 0 5.53 2.90 0.04 49 26 0

4.7 0.04

*

ficial uses which the water may be called upon t o supply, the quality of the ground water as unaffected by controllable pollutants, and the dilution factor which depends upon the rate of flow of ground water past the source of pollution, determine the capacity of the ground water t o absorb controllable pollutants. Typical analyses of waters which are believed t o be little affected by controllable pollutants are given in Table 11; their general locations are indicated on Figure 6. In some areas the ground water in its natural state contains excessive concentrations of harmful constituents. Under most conditions of soil and climate, boron in excess of about 0.5 p.p.m. in irrigation water has an adverse effect on the more sensitive crops (4). Boron is a common constituent of waters rising along December 1953

fault zones in the valleys or appearing as springs in the mountains and reaching the ground-water basins in the stream flow. Connate waters may also carry considerable boron derived from the materials in which they are held. Boron has been found in considerable concentration in wells located in the Cache Creek drainage area, along the west side of San Joaquin Valley in the Great Central Valley Area, in Simi Valley and Las Posas Valley in the south coastal area, and in Long Valley and Owens Valley in the Lahontan basin area. Authorities hold that drinking water in which the nitrate ion concentration is in excess of 40 to 80 p.p.m. should not be used by infants ( 7 ) . I n the course of a study of El Cajon Valley in San Diego County, to determine the effect of cesspools and private

INDUSTRIAL AND ENGINEERING CHEMISTRY

2661

of the ground-water level by excessive pumping is responsible. rlpproximately 90,000 acres of ground-water basins have suffered sea-water intrusion. Ocean Rater contains about 18,000 p.p.m. of chloride and between 10,000 and 11,000 p,p.m. of sodium, the ratio of sodium to total cations being on the order of 75 to 80%. The Cnited States Public Health Service standards for drinking water used on interstate carriers limit the desirable chloride concentration to250p.p.m. (11). A4gricultural authorities generally agree that concentrations of chloride in emess of 380 p,p.m, are undesirable in irrigation water, although waters materially higher in concentration are in use (5). +4ratio of sodium to total cations (in equivalents per million) in excess of 50 to 60y0 adversely affects manv soils (6). Figure 7 illustrates what has occurred n e a r M a n h a t t a n Beach in the west coast basin in Los Angeles County, owing to serious overdraft on the basin by the extensive industrial and municipal development ( 3 ) . The greater part of the present usable supply enters the basin as underflow from the central basin, in which the water table is itself drawn down almost to sea level. Raising the water level to produce an oceanward slope across the west coast basin would greatly reduce or Figure 5. Areas Covered in Special Investigations of Ground Water possibly eliminate this underflow. With this in mind, the maintenance of a ground-water septic tanks on the ground water, nitrates were found ranging up iidge along the coast, instead of an oceanir-ard slope entirely across the basin, has been proposed. As thick clay strata overlie the to 270 p.p.m. and exceeding 80 p.p.m. in samples from 80 of 260 greater part of the heavily pumped Silverado zone, injection of wells. The eflluent from the disposal installations probably conwater through wells would be required. Under contract with t.ibuted some nitrate, but as there was no correlation betm-een the State Kater Resources Board, the Los Angeles County Flood location of cesspools and concentration of nitrate and because the Control District is conducting a field experiment and the Univerapparent volume of the salts was so far in excess of that which sity of Califoinia is carrying out laboratory studies to determine could have originated in sewage wastes from the historic populathe feasibility of the proposal. The university is also studying tion, it was concluded that the condition was primarily native to some of the factors bearing on the feasibility of artificial imperthe valley. Movement of ground water through and out of the vious barriers and plans to investigate the effect of changes in valley is so small that the situation is analogous in some degree to pattern of pumping. In the case of some of the smaller basins, that in numerous closed desert basins, in the lower portions of economy may dictate the substitution of an imported supply as an which salt concentrations are very high. alternative to pumping from the ground water. Where this is done, In several areas of the state, ground waters of good native ground water of a qualltv suitable for use may still be available for quality have been degraded or replaced by naturally occurring inemergency use. To the extent that any of these remedies are ferior waters from adjacent areas or zones. While this is not polfeasible, degradation by the intrusion of sea water_is controllable lution under the restricted definition of Division 7 of the Code, At relatively shallow depth in several of these coastal basins, it is the result of human activity, and it can often be corrected. saline maters have been found overlying deeper strata of better Bordering the coast there are 80 ground-water basins which, bewater. In some cases nhere proximity to the ocean suggests cause of their location, are susceptible to intrusion by sea water sea-water intrusion as the cause of degradation of the deeper (2). Of these, 13 are believed to have been affected already in water, the true cause is infiltration of these perched ealine waters. some degree and in at least seven others the ground-water surface Samples collected from shallow holes in the coastal portion of Tia is so little above sea level that intrusion is threatened. Lowering

2662

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 45, No. 12

Industrial Process Water

.-

Juana Valley in San Diego County contained up to 10,000 p.p.m. of chloride ( 3 ) . Water at a depth of 100 feet in the vicinity contained about 500 p.p.m. Experience at an operating gravelpacked well nearby demonstrated the effect of interconnecting the strata. During about 8 months, chloride in the water pumped from this well increased from 518 to 720 p.p.m. At that time, pumping of the well was stopped, while continued pumping a t nearby wells maintained a . differential head between deep and shallow strata. Within 1 month, chloride in the idle well increased to 2010 p.p.m. Five months after pumping was resumed, the chloride concentration decreased to 705 p.p.m. One explanation is that during the period of shutdown, the poor-quality shallow waters invaded a considerable volume of the deeper zone and that in the succeeding period of pumping the greater part of this saline water was again drawn out, so that the resulting mixture of deep and shallow water pumped a t the well approached its original quality. Two factors-the interconnection of the strata through the gravel envelope and the development of a differential head through pumping from the deeper strata-were responsible for the invasion. Since the avoidance of a differential head would in this case, and in most similar situations elsewhere, preclude any substantial use of the ground water, the only feasible remedy is the establishment of an impervious seal be-

tween the zones. Wells with gravel envelope throughout and unfilled abandoned wells are dangerous in any situation where water quality varies widely in different strata. Connate brines underlie a considerable portion of the usable ground waters of the state, usually, however, at depths materially greater than the deepest of the water wells and usually separated from the usable water by relatively impervious zones of substantial thickness. Near Robbins, in Sutter County, water discharging under pressure from a n abandoned gas well 1500 feet deep contained 10.8 p.p.m. of boron, 1750 p.p.m. of sodium, and 3500 p.p.m. of chloride (9). Total solids were on the order of 6000 p.p.m. and the ratio of sodium to total cations was 74%. Throughout an area averaging some 5 miles wide and extending almost to Marysville approximately 20 miles to the north, the more shallow waters vary widely in salinity, total dissolved solids ranging from less than 350 to almost 2000 p.p.m. The character of the pumped water is such as t o indicate mixing of the better waters with the deeper brines, but studies to date have developed no conclusive evidence as to the manner in which such mixing may occur. A similar situation is under study at Stockton, where abandoned gas wells ranging in depth between 1000 and 3000 feet contain brines under pressure ( 3 ) . One objective of the study is to determine the probable effect of these wells on the usable water supply with continuance of the present heavy draft. POLLUTION EFFECTS

013

Figure 6 . Location of Wells Reported in Table I1

December 1953

INDUSTRIAL AND ENGINEERING CHEMISTRY

A l t h o u g h t h e r e is g r e a t variation with location and climate, most of California's native surface and ground waters are of good quality. They are suitable for industrial and other beneficial uses. These facts, and the sampling programs for c o n t i n u o u s l y checking water quality, are explained more fully in the preceding sections. But are these waters being protected against pollution so that they are suitable for beneficial uses without extensive treatment? In the following paragraphs d e g r a d a t i o n of quality caused by sea-water intrusion, return irrigation water, and sewage and i n d u s t r i a l waste is discussed. SEA-WATER INTRUSION. Investigations made by the Division of Water Resources show that degradation of fresh water supplies from sea-water intrusion has occurred in 13 major and minor ground-water basins along the coast and inland bay areas (2). As of 1950 sea-water intrusion had advanced inland in these basins from 0.125 to 4 miles. Much of ,the water underlying an area of about 90,000 acres has been rendered unfit for general use. The direct cause of sea-water intrusion in all instances may be a t t r i b u t e d to overpumping, which has reversed the normal seaward slope of the water

2663

I8000

200

I6000

100

14000

0

12000

W c

-100

10000

f

5 5

z

u

0

2

g z

-200

8000

3

3 W

P

-300

6000

-400

4000

-500

2000

o

600

IS^

iew

moo

3ow

3600

4200

4800

5400

6000

6600

7200

7800

3

0

FEET

Figure 7.

Sea-Water Intrusion at Manhattan Beach

table or the artesian-pressure surface. Furthermore, seven other chemicals derived from fertilizers and the soil. The Division of ground-water basins are seriously threatened. Water Resources will initiate studies in the near future to deterIntensive effort is being made to find a physical solution to the mine the extent of damage t o underground waters from this cause. SEWAGEAND INDUSTRIAL WASTES. The State and Regional problem. About $700,000 is being spent on an experimental project in the Manhattan Beach area of Los Angeles County to K a t e r Pollution Control Boards control pollution by setting determine if a fresh water ridge can be built up near the coastline regulations to govern discharges of sewage and industrial wastes. One of the premises of the California legislation is that these which will repulse and hold back the sea water. As corollary work, research projects on this and other forms of artificial regulations should be based on a case-by-case determination of barriers and the effect of changas in pattern of pumping are being whether pollution threatens or exists. It was intended that conducted by the University of California a t a cost of approxiregulations in each case would be established by a logical analysis matelg $30,000. of all pertinent factors. To decide each case on its own merits, the boards must know RETURN IRRIGAT~OS WATER. Surface water can suffer degradation of quality due to inflow from irrigation drainage. all the facts. Rather than chance the making of arbitrary (‘[Degradation” is often defined as an impairment to quality of decisions, the water pollution control boards have followed the water that is caused by the development, use, and re-use of the water itself. “Pollution,” ~ n used 4 in the general sense, includes degradation.) Irrigation \TrATER AND IRRIGlTION TABLE 111. EFFECT O F I S F L O W OF GROCND drainage water may contain high concentrations DRMN.4GE O S QUALITYO F M-ATER 1Y SA4SJOAQUIX RIVER of dissolved and suspended solids and is a major Sampling Point on San Joaquin River degradant to certain surface waters during periods Dos Maze Friant Mendata Palosb GraysonC Roadd Vcrnalk Determinationa of low stream flow. Kearly all major streams which 10-21-52 10-15-52 10-17-152 10-17-52 10-21-52 10-21-62 Date collected pass through areas of irrigated agriculture receive 64 66 64 68 64 61 Temperature, O F. return flow either as effluent seepage or as surface 6.9 7.1 7.4 7.7 7.7 7.6 pH b49 588 604 4 7 . 1 398 24.2 BC X 106 a t 25’ C. drainage. The effects of irrigation return on a given 31 29 23 44 2.1 4.2 Ca stream are marked by the increase in the content 13 13 2.5 0.9 8.5 0.7 Mg E4 64 43 123 4 . 3 2 2 S a of total solids with distance of flow of the stream 3.2 3.5 3.2 0.6 2.6 0.6 K from the mountains. Irrigation drainage also 119 119 98 185 12 21 HCOi changes the composition of surface flow in that there 48 41 29 116 2.2 1. o 804 95 83 153 54 1.8 3.4 C1 is generally an increase in the proportion of sodium 1.8 2.4 0.2 2.4 0.1 0.4 NO, chloride salinity. These changes may be observed 0.0 0.0 0.0 0.2 0.2 0.2 F 52 34 224 584 333 315 by comparing the analyses of water collected from Sum6 0.16 0.14 0.23 0.02 0.12 0.01 various points on the San Joaquin River between Boron 18 20 27 8.0 15 7.6 Silica Friant and Vernalis (see Table 111). This reach of 51 52 55 38 49 35 Sodium ’70 8 14 92 213 131 126 Hardneks, total the river receives both irrigation drainage and Hardness, noncar0 0 12 64 34 28 effluent seepage from the ground water during the bonate irrigation season together with large amounts of inFlow. cu. feet/ 350 0 I850 3 85 1360 secondf flow from tributary streams draining the Sierra 56 82 77 186 206 River mile ~ ~ . . 268 .. ..~ ~ hTevada. Regardless of the inflow from the triba Determinations in p.p.m. unless indicated otherxr-ise. b hIerced River tributary t o San Joaquin between Dos Palos and Grayson. utary streams, the increase in total solids in the C Tuoliimne River tributary t o San Joaquin between Grayson and Mane Road. d Stanivlaus River tributary t o San Joaquin between Maze Road and Vernalis. water between the upper and lower reaches is high. 8 Sum of determined constituents. Ground water may also be degraded through the f Flow in cubic feet per second is mean for day and is based on preliminary reports. B Flow not available as gaging station discontinued. return of percolating irrigation waters, which carry downward with them large amounts of dissolved

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INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 45, No. 12

-Industrial

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policy of getting the facts first. Regulations and enforcement are equally important in the control program, but they have had to play a secondary role during the first 2 years of operation. On the basis of more than 150 special studies sponsored by the pollution control boards during the first 3 years of operation, it is fair to generalize that there are only a few unsolved cases of extensive and gross pollution of surface waters due t o sewage and industrial wastes. There is a considerable number of waste discharges which affect limited local areas and water uses and which create unsatisfactory conditions. There are relatively few known instances of pollution of ground water in California, although some ground-water basins still show the effects of discharges that have been discontinued. Cases such as the “Montebello Incident,” where phenols in barrels and floor washings from a weedicide plant temporarily rendered downstream wells unfit for use, serve as a reniinder of the vigilance that must be maintained wherever land disposal of wastes is proposed or used. This does not mean that all present and future problems have been solved. Owing to the growing influx of population and industry, new problems are continually being created. Discharges which are trouble-free today may cause problems tomorrow because of changes in the waste or in land and water use. When completed, some of the special studies will undoubtedly demonstrate pollution where it is only suspected a t the present time, particularly in ground-water problems. FOURTEEN CRITICAL CASES. At its first meeting in 1949, the State Board was furnished a listing of 14 real or suspected critical water-pollution problems existing a t that time. Some of the problems were very extensive and involved discharge of mixed sewage and industrial wastes. Of these 14 cases, 7 have been virtually solved (including Los Angeles, San Francisco, and the East Bay area of San Francisco Bay), 2 are under construction, and 5 have been partially solved and are under further factual study. The unsolved problems all involve both sewage and industrial wastes. Modesto, which has a population of 20,000 and a seasonal population equivalent of 400,000 due t o cannery discharges, needs additional treatment facilities. Untreated sewage and industrial wastes are discharged into South San Francisco Bay in the vicinity of San Jose, causing periodic gross pollution of the bay waters and odor nuisances in nearby communities. Although most financing and engineering plans have been completed, the principal problem (that of waste discharge from San Jose) is being delayed by condemnation proceedings over the plant site. The communities of Richmond, Stege, and San Pablo discharge untreated wastes into San Francisco Bay. Engineering plans are ready, or are under preparation, for Richmond and Stege. Factual studies have been completed on the pollution problems of the Los Angeles-Long Beach Harbor. Similar studies are being continued along the Los Angeles River. Using the data from these studies, the regional board will formulate basic policy for the control of pollution in these two problem areas. INDUSTRY ACTIOX. Industries have built many waste-treatment and disposal facilities where discharge of their wastes has not been through community systems. At least 86 industrial plants have constructed waste-treatment and disposal units. More detailed information on industry action and progress, on self-improvement programs of industry, and on by-products recovery is given in an official report of the water pollution control boards to the 1953 Legislature (8).

December 1953

’

Process Water SUMMARY

An entirely new and different concept-case-by-case study of problems-was embodied in the California Water Pollution Control Act of 1949. To make such an approach work, all facts surrounding each case must be known, including characteristics of waste and quality and use of surface and underground waters. Because of the wide variation in geologic complex, climate, and other factors, i t is difficult to generalize on the geochemistry of the natural waters of California. T o obtain data for use in measuring changes in water quality due to pollution, the state has initiated a monthly sampling program a t 148 stations on 88 major streams and lakes. Physical, chemical, bacteriological, and radiological determinations are made on these samples. Approximately one half of the water used in California comes from ground-water basins. Although intensive studies have been conducted in over 40 problem areas, systematic study on a statewide basis of ground-water quality is still in the planning stage. Studies to date show that most of California’s native surface and ground waters are of good quality. Ninety per cent of the waters would class as low to moderate in mineral content. Degradation of native waters is caused by sea-water intrusion, irrigation drainage water, and sewage and industrial wastes. Much of the water underlying an area of about 90,000 acres has been rendered unfit for general use by sea-water intrusion. Irrigation waters draining from or passing through soil cause considerable mineralization of both surface and ground waters. On the basis of over 150 special studies, i t is fair to generalize that there are only a few unsolved problems of gross pollution of surface waters due t o sewage and industrial wastes, and there are relatively few known instances of pollution of ground water from that source. Both industries and communities have done commendable jobs in correcting and preventing pollution. During the past 3 years, 170 communities have constructed sewerage facilities a t a total cost in excess of $163,000,000 and 86 industrial plants have constructed waste-treatment and disposal units. ACKNOWLEDGMENT

Special thanks are extended to C. S. Howard, regional chemist, U. S. Geological Survey, for his assistance on the section on geochemistry, to A. D. Edmonston, state engineer and chief of the Division of Water Resources, for review and clearance of the paper, and to W. W. Hastings, assistant chief, Quality of Watter Branch, U. S. Geological Survey, for review and clearance of the paper. LITERATURE CITED

(1) Am. Public Health Assoc., New York, “Standard Methods for

the Examination of Water and Sewage,” 9th ed., 1946. (2) California Division of Water Resources, Water Pollution Investigations, Rept. 1 (December 1950). (3) California Division of Water Resources, unpublished data. (4) California State Water Pollution Control Board, Pub. 3, 149 (1952). ( 5 ) Ibid., p. 150. (6) Ibid., p. 153,2nd para. (7) Ibid., p. 301,2nd para. (8) California State and Regional Water Pollution Control Boards, Pub. 5 (December 1952). (9) California State Water Resources Board, Bull. 6 (September 1952). (10) Hannum, W. T., IND.ENQ.CHEM., 45,2652 (1953). (11) U. S. Pub. Health Service, Pub. Health Repts., 61,371-84 (1946). RECEIVED for review June 22, 1953. ACCEPTEDSeptember 14, 1953.

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