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Ivan Barnes

Publications and source records attributed to Ivan Barnes.

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Chemical properties of ground water and their corrosion and encrustation effects on wells

Well waters in Egypt, Nigeria, and West Pakistan were studied for their chemical properties and corrosive or encrusting behavior. From the chemical composition of the waters, reaction states with reference to equilibrium were tested for 29 possible coexisting oxides, carbonates, sulfides, and elements. Of the 29 solids considered, only calcite, CaCO 3 , and ferric hydroxide, Fe(OH) 3 , showed any correlation with the corrosiveness of the waters to mild steel (iron metal). All 39 of the waters tested were out of equilibrium with iron metal, but those waters in equilibrium or supersaturated with both calcite and ferric hydroxide were the least corrosive. Supersaturation with other solid phases apparently was unrelated to corrosion. A number of solids may form surface deposits in wells and lead to decreased yields by fouling well intakes (screens and gravel packs) or increasing friction losses in casings. Calcite, CaCO 3 ; ferric hydroxide, Fe(OH) 3 ; magnetite, Fe 3 O 4 ; siderite, FeCO 3 ; hausmannite, Mn 3 0 4 (tetragonal); manganese spinel, Mn 3 O 4 (isometric); three iron sulfides mackinawite, FeS (tetragonal); greigite, Fe 3 S 4 (isometric); and smythite, Fe 3 S 4 (rhombohedral)-copper hydroxide, Co(OH) 2 ; and manganese hydroxide, Mn(OH) 2 , were all at least tentatively identified in the deposits sampled. Of geochemical interest is the demonstration that simple stable equilibrium models fail in nearly every case to predict compositions of water yielded by the wells studied. Only one stable phase (calcite) was found to exhibit behavior approximately predictable from stable equilibrium considerations. No other stable phase was found to behave as would be predicted from equilibrium considerations. All the solids found to precipitate (except calcite) are metastable in that they are not the least soluble phases possible in the systems studied. In terms of metastable equilibrium, siderite and ferric hydroxide behave approximately as would be predicted from equilibrium considerations, but both are metastable and the presence of neither would be anticipated if only the most stable phases were considered. The behaviors of none of the other solids would be predictable from either stable or metastable equilibrium considerations. An unanswered problem raised by the study reported here is how, or by what paths, truly stable phases form if first precipitates are generally metastable. The utility of the findings in well design and operation is in no way impaired by the general lack of equilibrium. Conditions leading to either corrosion (which is related to lack of supersaturation with protective phases), or encrustation (supersaturation with phases that were found to precipitate), or both, apparently can be identified. The application of the methods described can be of great importance in developing unexploited ground-water resources in that certain practical problems can be identified before extensive well construction and unnecessary well failure.

Professional Paper

Water-mineral relations of Quaternary deposits in the Lower Platte River drainage area in eastern Nebraska

The partial pressure of carbon dioxide (PCO2), the degree of saturation with respect to calcite (IAP/K calcite), the pH, and the concentrations of selected constituents in solution were determined for water from 52 wells and the Platte River. Compared to the PCO2 in the atmosphere, the average PCO2 in the ground water was many times greater and that in .the river water was about twice as great. The high PCO2 in the ground water probably results from the absorption, by infiltrating precipitation, of carbon dioxide produced in the soil by respiration of plant roots ,and microorganisms. The values for IAP/K calcite for the ground water ranged from 0.141 to 1.29 and for the river water the average was 9.6. Water from each of the 10 sampled wells on the terrace plain in southeastern Saunders County was unsaturated with respect to calcite, whereas water from seven of the 42 wells on the Platte River flood plain was nearly saturated or supersaturated. Of the ,seven, two were in the Lincoln city well field where hydrologic relations indicate that a large fraction of the water yielded by the wells is induced seepage from the .river. That more of the city wells did not yield supersaturated water is surprising in view of the high IAP/K calcite values for the river water. Supersaturation of water from five of nine sampled wells downvalley from the well field probably is due to the presence of numerous limestone fragments in the Quaternary deposits in that part of the area. also surprising was the finding that the average pH of the water from the city wells was 1 unit lower than that of the river water. The presence of both dissolved iron and dissolved oxygen in the water from several of the city wells probably reflects derivation of the water from two distinct sources : ground water naturally in the aquifer and induced seepage from the river.

Water Supply Paper

Relation of electrochemical potentials and iron content to ground-water flow patterns

This study was undertaken to develop means of measuring oxidation potentials in aquifer systems and to use the measured values in interpreting the behavior of iron in ground water. Anne Arundel County, Md., was selected as the area of study because of the wide range of concentration of iron-nearly zero to about 35 ppm-in the ground water and the rather complete information on the geology and hydrology. The regional geology consists of coastal plain sediments ranging in age from Early Cretaceous through the Recent. Most of the pH and oxidation-potential measurements were made in nonmarine Cretaceous deposits, only a few in the marine Eocene. Iron-bearing minerals in the area are primarily hematite or limonite and glauconite with a small amount of pyrite. Equipment was developed that permits the measurement of oxidation potentials by use of saturated calomel and platinum electrodes in ground-water samples uncontaminated by oxygen of the atmosphere. Measured Eh values range from about +700 mv to -40 mv. Approximately 2 to 3 hours are required to measure a stable or nearly stable oxidation potential. The mineralogy and organic content of the deposits and the ground-water flow pattern are the primary controls on the oxidation potential and pH of the water. A correlation exists between the oxidation potential and the concentration of iron in ground water; the higher concentrations occur in waters with the lowest values of Eh. The concentration of iron in the water tested shows little correlation with the pH of the water. The highest oxidation potentials were measured in water produced from shallow wells and those wells in recharge areas. The lowest potentials were measured farthest downgradient in water associated with gray and green sediments. The Eh values measured in the field are between values predicted from the solubility of Fe(OH) 2 (c) and values predicted from the solubility of hematite.

Maryland

Field measurement of alkalinity and pH

The behavior of electrometric pH equipment under field conditions departs from the behavior predicted from Nernst's law. The response is a linear function of pH, and hence measured pH values may be corrected to true pH if the instrument is calibrated with two reference solutions for each measurement. Alkalinity titrations may also be made in terms of true pH. Standard methods, such as colorimetric titrations, were rejected as unreliable or too cumbersome for rapid field use. The true pH of the end point of the alkalinity titration as a function of temperature, ionic strength, and total alkalinity has been calculated. Total alkalinity in potable waters is the most important factor influencing the end point pH, which varies from 5.38 (0 ? C, 5 ppm (parts per million) HC0a-) to 4.32 (300 ppm HC0a-,35 ? C), for the ranges of variables considered. With proper precautions, the pH may be determined to =i:0.02 pH and the alkalinity to =i:0.6 ppm HCO3- for many naturally occurring bodies of fresh water.

Water Supply Paper