Waste-Water Injection: Geochemical and Biogeochemical Clogging Processes by June A. Oberdorfer* and Frank L. Peterson? ABSTRACT Examination of near-wel clogging processes at two experimental injection sites in Hawaii shows that filtration of suspended solids is not a long-term cause of clogging. While particulate filtration is probably a short-term cause of clogging at the start-up of injection, the injected organics are biodegraded once the microbial biomass becomes. established. The injection head gradient determined from monitoring wells shows that most of the initial head loss is immediately adjacent to che well, but that after several weeks it shifts to a region over 0.5 m from the well. Denitrifying bacteria become sufficiently numerous to produce significant amounts of nitrogen gas, which in turn produces a gas-bound zone about 0.5 to I m from the well, With continued injection the nitrogen gas-bound zone is slowly extended farther out into the injection stratum, Dissolution of the carbonate aquifer also occurs, but its effects are partially masked by gas binding. INTRODUCTION Waste-water disposal into injection wells almost inevitably produces aquifer clogging and reduced injection capacity. In Hawaii, overflows from wells injecting secondary treated sewage effluent have created numerous public health, legal, and financial problems. To determine the causes of clogging, geochemical and biogeochemi- assistant Professor of Hydrogeology, San Jose State University, San Jose, California 95192, Professor of Hydrogeology, Department of Geology & Geophysics: and Researcher, Water Resources Research Center, University of Hawaii at Manoa, Honolulu, Hawaii 96822 Received July 1984, accepted May 1985. Discussion open until May 1, 1986, Vol. 23, No. 6~GROUND WATER-November-December 1985 cal processes that occur in the near vicinity of the injection well were examined utilizing observation well and sediment core and pore-water analyses, Although injection wells are widely used in the United States and throughout the world for waste disposal and artificial recharge, few detailed investigations of injection well clogging processes have been reported. Probably the most compre- hensive study is a compilation by Olsthoorn (1982) of clogging problems associated with recharge wells, Other studies most pertinent to this work are examination of injection well problems in Hawaii by Petty and Peterson (1979), aquifer clogging caused by the injection of primary treated sewage effluent at Richmond, California (California Water Pollution Control Board, 1954), and clogging at Bay Park, New York as a result of injection of tertiary treated sewage effluent (Ehrlich et al. 1972; Bhrlich et al., 1977; Ragone, 1977; Vecchioli and Ku, 1972; Vecchioli et al., 1980) ‘The most significant conclusions from these studies are the following: 1. The major cause of clogging at most of these sites is filtration by the porous media of suspended solids contained within the injectant. 2. The second major cause of clogging results, from microbial growth at the well face and within the aquifer. 3. Of lesser significance are chemical precipi- tation processes. 4. On occasion, clogging may result from entrapped air and gas bubbles introduced by the injectant. 5. Most of the clogging activity occurs at or very near the injection well-aquifer boundary, and 753in many instances a mat of filtration material forms directly on the aquifer surface. The above conclusions were the preconcep- tions with which we commenced this study. As our research developed, they proved to be less relevant to the Hawaiian injection environment than originally thought. Other processes, particularly biogenic nitrogen gas binding, appear to be more important for well clogging in the Hawaiian injection situations studied. DESCRIPTION OF FIELD SITES AND EXPERIMENTS Despite the recognition that clogging occurs in the near vicinity of the well, no previous investi- gations have examined sediment samples or pore water taken ftom the injection formation within the first few meters of the well. The nearest observation wells are generally located several meters from the injection well. To obtain more direct evidence of the processes occurring in this very near-well environment, two experimental injection sites were installed and numerous data were collected and analyzed. The most useful of these included measurements of injection head distribution, analyses of sediment cores taken from the injection strata, and analyses of water collected from the injection strata (pore water). ‘The experimental sites were selected to dupli- cate as closely as possible the general conditions at operating Hawaiian injection sites. Most disposal wells in the Hawaiian Islands inject secondary- treated sewage effluent into coastal plain aquifers consisting of marine carbonate and alluvial sedi- ments or highly permeable basaltic flows, all gener- ally saturated with brackish water. The wells range typically in diameter from 0.10 to 0.15 m, are less than about 30 m deep, and have injection rates less than 6.3 X 10 ms per well. The injection experi- ments described were all conducted into a fine carbonate sand aquifer (Waimanalo) and a coral reef and rubble aquifer (Paalaa Kai), Site A This site is located on the grounds of the Waimanalo Wastewater Treatment Plant at Waimanalo, Oahu, Hawaii. The injection formation at this site is a fine to medium carbonate sand layer approximately 3 m thick, overlain by a dense impermeable clay layer and underlain by a low- permeability clayey coral rubble layer. The hydraulic conductivity of the sand layers was determined by pump testing to be about 3.5 x 10% m/s. This formation, which is representative of 754 some of the least permeable receiving formations available for waste disposal in Hawaii, was selected for these experiments because of its susceptibility to clogging. Five injection wells, three of 0.10 m diameter and two of 0.15 m diameter, were utilized for injection experiments. All of the injection wells were cased with PVC pipe and slotted throughout their entire length. Figure 1 shows the location of injection wells, observation wells, and sampling sites. Figure 2 shows a hydro- geologic cross section through the three wells where sediment samples were collected. The injectant was secondary treated domestic sewage which contained BOD. averaging about 10 to 15 mg/t, suspended solids of 5 to 15 mg/t, and total chlorine residual of 1.5 mg/2. Injection experiments were conducted from May 1980 to June 1982, Sediment cores were taken adjacent to Well 4-5 in October 1980 after five months of injection, and additional cores were collected at Wells 4-4 and 6-2 in April 1981. Observation wells were installed in each of these latter coring sites. Cores were taken at 0.3, 0.6, and 0.9 m from the injection well and at depths of 2.4 and 2.7 m below ground surface. Site B ‘This site is located on the grounds of the Paalaa Kai Wastewater Treatment Plant, Waialua, Oahu, Hawaii. The injection formation is a 3m thick layer of coral and recemented reef rubble lying at a depth of 11 to 14 m below ground surface. This formation is much more permeable than the one at Waimanalo and has a hydraulic conductivity of about 0.01 mys. It is representative Fig, 1, Waimanalo experimental well layout and sampling sites, Oahu.Lat moeete Fig. 2. Cross section at Site A Wai of some of the better sedimentary receiving forma- tions on Oahu. One injection well (PK-1) and three observation wells (at 0.6, 1.3, and 2.0 m from the injection well) were used. Like the Waimanalo wells, PK-1 is cased with 0.10 m PVC casing slotted throughout its entire length, The injectant is of excellent quality, having been filtered through a rapid sand filter after receiving biological secondary treatment. The BOD; and suspended solids averaged less than 5 mg/£. Injection took place from July 1981 to June 1982 METHODS Sediment samples were collected with a hand auger. Water from the observation wells was sampled at the pump discharge or with a thief sampler after sufficient bailing to remove the water originally in the well bore. The injectant was sampled at the discharge into the well. A complete description of chemical analytical methods is given in Oberdorfer (1983) or Oberdorfer and Peterson (1982), Briefly, sediment analyses included: 1. ATP-Biomass Index: Two cc of sediment were injected into 10 me boiling phosphate buffer to extract ATP. Analysis performed on SAI Tech- nology Co. ATP Photometer Model 200 (see Karl and LaRock, 1975), 2. Iron: Sample was ashed at 550° C for 4 hr to remove organics. Sample then digested in acids ina teflon crucible (see Bernas, 1968). Detection by atomic adsorption (APHA et al., 1980), Part 301A with standard addition. analo Wells 4-4, 4-5, 6-2, including observation wells and sampli 3. Organic Carbon: Performed on a Hewlett Packard 185-B carbon and nitrogen analyzer (see Smith et al., 1981) Pore-water samples were obtained with a thief sampler except in the case of dissolved ‘oxygen which was measured in the well. Analyses include. 1, Alkalinity: APHA Part 403 2. Chlorides: APHA Part 408A. 3. Dissolved Nitrogen (ammonia, nitrate/ nitrite, total): APHA Part 604 on a Technicon Autoanalyzer I] after filtration with a 0.45 m ‘membrane filter. 4. pH: Measured with a Photovolt pH Meter 126A, calibrated with pH 7 and pH 10 buffer. 5. Dissolved Oxygen: Measured with a YSI Model $7 Oxygen Meter. 6, Dissolved Nitrogen Gas and Methane Gas: 5 me samples taken immediately from the thief sampler with a glass syringe; dissolved gas extracted into 5 me of cartier gas (helium) in syringe head space during one minute of agitation; head space gas then run through gas chromatograph with 1.8 m by 0.003 m OLD. stainless steel column filled with Molecular Sieve $-A-80/100 and measured with thermal conductivity; procedure slightly modified from Martens and Van Klump (1980). 7. Dissolved Cations (calcium, magnesium, strontium): Samples filtered with a 0.45 m membrane filter and analyses performed by inductively coupled plasma spectroscopy (see Peck et al., 1979) 755DISTANCE FROM WELL (m) IC HEAD (m-s /m? x 10%) SPECI WELL |, Paalaa Kai Well PK-1, 23, Specific hydraulic hes RESULTS AND DISCUSSION Formation Head Distribution With a number of observation wells close to the injection well, the head distribution within the injection stratum in the near vicinity of the well can be monitored and its evolution with time observed. Figure 3 shows the specific head buildup (injection head buildup divided by the injection rate) for the site B well at various times during its injection history. These times included: at the initial fresh-water injection test, twice shortly after the start-up of injection, and twice after prolonged petiods of injection. The Site A wells showed similar patterns. ‘The head distribution curves for the wells indicate that a maturation process occurs in the injection stratum over the first several weeks after the startup of injection. The head buildup at the time of the fresh-water injection test for each of the wells represented a normal appearing cone of impression. The major head loss was observed immediately adjacent to the well and the gradient leveled off with distance. In the first few days after the start-up of injection, head loss increased immediately adjacent to the well. An increase in head loss indicates a decrease in hydraulic con- 756 ductivity, ie., clogging. Thus, during the first few days of injection, virtually all of the clogging took place immediately adjacent to the well and there was little indication of any clogging beyond the first observation well. As injection continued, there was a shift outward of the clogging. Although head loss remained significant adjacent to the well, a marked increase in head loss beyond the first observation well was observed after eight days. Clogging was now occurring in a zone farther out from the injection well. This outward progression of clogging proceeded thereafter at a more gradual rate. Ultimately almost no head loss occurred in the zone nearest the well where almost all of the initial head loss took place. This decreased head gradient indicates an increase in permeability over initial conditions and may indicate dissolution of the porous medium, At all of the observed wells, the clogging initially occurred in a zone within about 0.5 m from the injection well. After a few weeks to a month of injection, most of the clogging occurred in a zone anywhere from 0.7 to 1.3 m from the injection well. Figure 3 also shows the effects that redevelop- ment can have on head distribution. Redevelop ment by acid treatment and pumping after the January 1982 observations produced a lower specific head and a reduction in head as far out as observation well PE2 (0.6 m from the injection well), The effects of redevelopment probably extend a meter at this site, although in general the effectiveness of redevelopment will depend on which redevelopment technique is used. For this well the clogging did not extend beyond 2 m. This limit was also true for most of the Site A wells, except for one in which the clogging extended well beyond 2 m. Sediment Cores Because particulates in the injectant were expected to play a major role in clogging, the accumulation of particulates in the sediment was closely examined. Sediment cores were taken from the injection strata adjacent to three of the wells at Site A, each within a meter of the injection well. Figure 4 shows the concentration of several of the ‘most significant constituents in the sediment cores as a function of distance from the wells. As described previously, the samples were collected after several months of injection so the clogging processes were well established. The points plotted in this figure are averages of analyses of two samples collected at slightly different depths at each coring site. Since multiple analyses were frequently performed on each sample, a pointoften represents the average of more than two data, Depth may affect some processes, particular- ly where closeness to the water table might play a role; however, no consistent pattern of variation with depth was observed. A large variability frequently occurs in values obtained for a single parameter at a given coring site. This is a result of the variability found in natural systems, and is typical of environmental sampling. Microbial biomass (measured as ATP) is particularly susceptible to environmental variability. To under- stand the system, the major trends should be observed, rather than focusing on a single anomalous result. Background samples were collected at three locations relatively far from the injection wells and their averages are plotted to the right-hand side (Figure 4) for comparison Generally, the sample farthest from the well fea ie - ho qT : : ae tes § Het # cecmee = awnes wena DISTANCE FROM WELL (m) Fig, 4, Concentration of selected constituents in sediment samples from Site A vs, distance from well (0.80-0.94 m) had concentrations similar to the background samples. Cores taken closest to the well showed the greatest difference from back- ground levels. This is to be expected as the processes involving particulates are initiated by filtration and thus take place immediately adjacent to the well Percent organic carbon in the sediment asa function of distance from the well revealed a deple- tion of organic carbon adjacent to the well. This depletion was unexpected ; instead an increase in organic carbon from accumulation of injected particulate matter was expected to occur (the injectant has a suspended solids load of 10-15 mg/t of which 95% is volatile, i., organic) Particulates have long been considered to be a major cause of clogging, but these data contradict that. The most probable explanation of the near- well depletion is that the microbial population metabolizes all of the organic carbon put into the system plus, due to the high metabolic rate induced near the well, the refractory compounds which persist at a greater distance from the well. Organic carbon concentrations at 1 m are similar to background concentrations so there does not appear to be an accumulation of particulates that have simply travelled farther out into the formation. The mictobial biomass (ATP) nearest the well is an order of magnitude greater than background levels. The large error bars on this plot reflect the variability found in environmental samples; how- ever, major trends are still clearly discernible, Injectant ATP levels of 0.5 to $ ng/me would not account for this biomass accumulation by simple filtration, This biomass increase in a nutrient-rich environment indicates that most of the metabolism of organics occurs very close to the well and is consistent with the organic depletion discussed above, The bacteria at 1 m, while not quantitatively significant, are qualitatively significant, particularly in mediating redox reactions. he injectant chlorine residual (averaging 0.5 to 3.0 mg/t) decreases but is still detectable at 1 m from the well, yet the bacterial community can persist, even fluorish, in the chlorinated environment. They may inhabit more protected microenvironments, such as in cavities in the sand grain surfaces or at contact points between grains, where they would be less exposed to continuous contact with the high chlorine residual. Immediately adjacent to the well, bulk density increases markedly due partially to the addition of fine particulate matter which can be seen in the sediment cores as a brown discoloration 757at the time of sampling. Iron, aluminum, and phosphorus also show increases in this region. Part of this fine particulate matter is present as iron monosulfide, The sulfide is produced by biologically mediated sulfate reduction which must occur in microenvironments in the porous medium since sulfate-reducing bacteria are strict anaerobes and could not survive in the aerated bulk pore water. The hydrogen sulfide quickly reacts with iron in the system to form iron monosulfide, The iron levels are much greater at the 10-mo sampling (Wells 4-4 and 6-2) than at the 5-mo sampling (Well 4-5), indicating that this iron accumulation is arate dependent process. Additional iron is present in iron-rich clays (typical in Hawaii) which are introduced with the injectant and filtered out shortly after entering the system. ‘To summarize, analyses of sediment cores indicate that particulate processes occur in the first few tens of centimeters from the injection well, but at a distance of a meter away there is little to distinguish the sediments in the injection stratum from background samples. An increase in biomass occurs adjacent to the well where there is a high nutrient influx, but it does not appear to be massive enough to be a major cause of clogging. This is supported by detailed microscopic examina- tion of the sediment cores and by the injection head data described earlier. In the first days after injection start-up, head increased immediately adjacent to the well, probably because particulate organics accumulated there before the microbial population became well enough established to consume all of the incoming particulates. It should be remembered, however, that after a few weeks the zone of high head loss, and hence clogging, shifted farther outward from the injection well (Figure 3), We think this occurred when the micro- bial population became well enough established after the first few weeks to metabolize the organics which had accumulated near the well, thus reducing the clogging there. To be sure, deposition of fine particulate matter, as indicated by the bulk density increase, was observed adjacent to the well throughout the injection experiments. However, the deposition was not massive enough to substantially increase clogging, and the loss of permeability caused by the addition of these particulates seems to be overshadowed by dissolu: tion of the carbonate aquifer. Thus the results from our work suggest that although clogging by particulate matter may be important for the first few weeks of injection, it apparently is not a major contributor over the long run. 758 Pore Water Analysis of the sediment cores has mainly indicated what does not cause clogging. To deter- mine what is causing the clogging, it is necessary to examine the pore waters taken directly from the injection stratum, ‘Thus, pore-water samples were collected several different times and analyzed for over 25 different constituents. Given here is a summary of only the most significant results. The complete data set is available in Oberdorfer (1983). All of the pore-water data presented in this paper were collected after extended periods of injection. During this time chloride levels in the formation water in the near vicinity of the wells (2-20 m) were identical to the levels in the injectants and significantly lower than chlorides in the native ground water prior to the start-up of injection. Since chloride is a conservative tracer whose concentration does not change in the forma- tion except by mixing with waters of different chloride concentration, the results indicate that the effluent has displaced all of the ground water in the vicinity of the well, and dilution effects cannot account for changes in formation water quality. Figure 5 shows the concentration of several key pore-water constituents versus distance from the injection well (zero distance represents the injected effluent). Since the injectant quality can be highly variable, concentrations are expressed in terms of changes from input concentrations, as the changes in water quality reflect the processes occurring. Additional wells sampled at Site A showed similar trends. The error bars are in large part a reflection of sample variability for different sampling times, often a result of injectant concen- tration variability. Again, major trends rather than details should be noted. The data from Figure 5 suggest that there are two processes of major significance to clogging which occur immediately adjacent to injection wells. The first of these is dissolution of the carbonate aquifer material, a process that actually decreases rather than increases clogging potential. The injectant is mildly acidic which contributes to carbonate dissolution In addition, bacterial metabolism of the injected organics consumes oxygen (see decrease in dissolved oxygen with distance from well in Figure 5) and produces carbon dioxide and water which rapidly convert to carbonic acid. Carbonic acid dissociates to bicarbonate and hydrogen ions in the pH range in question, as shown by equation (1). CH,O +0, = CO, +H,0=H,CO,=HCO3 +H". (1)pH ALKALINITY (mg/2) bissoLveo CALCIUM (mo/2) pissoived ‘OXYGEN (me/2) 0 Site 8 Well PK-1 © Site Well 4-4 % 15 75 DISTANCE FROM WELL (m) Fig, 5. Concentration of selected constituents in pore water fance from well. This would be expected to cause the pH to decrease. However, the pH increases because carbonate solution neutralizes the acid, by the reaction, HY + CaCO, = Ca"* + HCOS, 2) ‘This reaction increases the pH, alkalinity, and calcium concentration, all of which are shown in Figure 5 to increase with distance outward from the well. The saturation indices (a measure of the aggressivity of water towards a given mineral) for the pore water sampled indicate that the water is undersaturated with respect to calcite and aragonite. At the current rates of dissolution based on the calcium results and typical flow rates (3X 10% ms at Site A, 7 X 10? ms at Site B), between 0.7 and 7% of the carbonate porous medium is lost each year from the near-well region, The second process of major consequence for injection well clogging is the production of nitrogen gas by denitrifying bacteria which leads to gas binding of the aquifer pore spaces. Nitrogen species concentrations are given in Figure 6 Dissolved organic nitrogen was determined to be insignificant so that total dissolved nitrogen has been calculated as the sum of ammonia nitrogen and nitrate + nitrite nitrogen. Organically bound nitrogen in the domestic waste water is bacterially decomposed to ammonia. The ammonia, in the presence of oxygen and nitrifying bacteria, is oxidized first to nitrite and then to nitrate, according to the reaction, NH; + 20; = NO, + 2H" H,0 @B) which does not show the intermediate step to nitrite. Under mildly reducing conditions and in DissoLveD AMMONIA (mg-N/2) (mo-N/2) DissowveD CALCULATED TOTAL DISSOLVED NITRATE/NITRITE Soturation) NITROGEN (mg/2) NITROGEN GAS © Site A, Well 4-4 © Site 8 Welt Pk-1 z 15 7 DISTANCE FROM WELL (m) Fig, 6, Concentration of nitrogen species in pore water vs. distance from well, 759the presence of organic matter, nitrate + nitrite can be removed from a system by bacterially mediated denitrification producing nitrogen gas, as shown by the reaction, CHO 4 4/5 NO3= 2/5 Na +HCO, +1/5 H+2/5 H,0 4) Because of the source/sink relationship between ammonia and nitrate + nitrite, total dissolved nitrogen (TDN) should be considered when evalu- ating nitrogen removal from an aqueous system ‘The TDN provides 2 measure of the dissolved organic, ammonia, and nitrate + nitrite nitrogen in the system, but not the gaseous forms, The TDN curves show significant decreases outward from the wells, as do the ammonia and nitrate + nitrite curves. Since nitrogen loss to cation exchange or bacterial uptake should be minimal in the quasi- steady-state system after one to two years of injection, the only reasonable cause for nitrogen removal from the TDN is denitrification. In Well 4-4 most of the decrease takes place in the zone between 0.53 and 0.91 m (the zone where most of the clogging occurs), while at PK-1 the de- crease appears to occur uniformly over the 2m radial distance monitored. Nitrogen gas, the end product of denitrifica- tion, increases in concentration with distance out- ward from the well. The data were somewhat erratic due to the difficulty of sampling for nitrogen gas without contamination by atmo- spheric nitrogen. The decrease in TDN, however, provides a positive indication for nitrogen gas pro- duction by denitrification, Furthermore, methane gas was also detected in some of the pore waters at site A at concentrations up to 1.5 mg/@. Methane production occurred primarily in those zones where there was a major decrease in TDN Methanogenic bacteria are strict anaerobes and produce methane gas only in strongly reducing environments. Again, this is a strong indication that these bacterial reactions take place in micro- environments as the methanogenic bacteria could not tolerate the oxygen in the bulk pore water. It also indicates that enough exchange occurs between microenvironments and bulk pore water for the anaerobic microenvironment processes to affect the bulk pore-water quality. Thus, while the amount of methane detected was small, itis quali- tatively significant because, thermodynamically, denitrification should precede methane produc tion. So while methane in itself does not make a significant contribution to clogging, its presence is 760 important as an indication that denitrification reactions are likely to be taking place. ‘The injectant was well aerated during treat- ment and could expectedly be close to nitrogen gas, saturation, As nitrogen gas concentration increases because of denitrification, the N, will become supersaturated (saturation is approximately 14 mg/t at pore-water temperature of 25°C and pressures found in the injection formation). A portion of the nitrogen gas will come out of solu- tion and form gas bubbles. The gas bubbles can cause gas binding of the porous medium by blocking the pores in the same way that a particle would. Lance and Whisler (1972) and Rice (1974) concluded that the major reduction in hydraulic conductivity observed in soil columns saturated with secondary-treated effluent was caused by nitrogen gas binding, Nitrogen removal from Lance and Whisler's columns averaged 34%, which is approximately the amount removed up to the farthest-out observation well at both sites. Using the total dissolved nitrogen results and typical flow rates, crude calculations were made as to how fast nitrogen gas production could cause clogging of the aquifer. Calculations for Well 4-4 indicated it would take roughly 60 days for the zone between 0.5 and 0.9 m to become completely gas bound and about 30 days for its porosity to be reduced by 50%. Since it is quite likely that some of the bubbles escape, these time periods are probably too short, but they should give an idea of magnitude for the rate at which clogging would occur. They also match well with the measured rates of clogging at this site. CONCLUSIONS Under the conditions that prevailed during this study (injection of secondary-treated sewage effluent into carbonate receiving formations) filtra- tion of suspended solids does not appear to be a long-term cause of clogging, a finding contrary to results commonly reported in the literature. Although filtration was not a long-term cause of clogging, itis very likely to have short-term clogging effects. An interpretation that is consis- tent with our data is that in the first days after the start-up of effluent injection, the head gradient that was observed to increase in the region immediately adjacent to the well was most likely due to the filtration of injected suspended solids in that region, ‘The microbial population was not yet established and thus could not biodegrade the largely organic injected particulates. After the bacterial colony established itself over the first fewweeks of injection, two significant changes that affect clogging occurred, First, the bacterial popu- lation immediately adjacent to the well metabo- lized all of the injected particulate organic matter, thus removing much of the clogging from this region where all of the clogging initially took place. Second, when the denitrifying bacteria became sufficiently well established, they produced signifi- cant amounts of nitrogen gas, which resulted in a gas-bound zone farther out in the aquifer. This was revealed by the steep head gradient which became ‘established over half a meter out from the injection well in a zone where there was originally almost no head loss. With continued injection, the nitrogen gas-bound zone slowly extended farther out into the injection stratum, Superimposed on this, but with its effects masked in part by the gas binding, was dissolution of the carbonate porous medium. The increase in permeability that resulted from carbonate dissolution in the non-gas-bound region near the well caused the flattening of the head gradient immediately adjacent to the injection well, The high degree of clogging created farther out in the aquifer by denitrification overrode the permeability increase caused by carbonate dissolu- tion, and the wells underwent major losses of injec tion capacity. While this is not the only possible scenario for clogging to occur, it is strongly supported by repeated patterns at both of the injection sites studied and certainly warrants further investigation. REFERENCES American Public Health Association, American Water Works Association, and Water Pollution Control Federation. 1980, Standard Methods for the Exami- nation of Water and Wastewater. 15th ed. APHA, AWWA, and WPCF, Washington, D.C. Bernas, B. 1968. A new method for decomposition and comprehensive analysis of silicates by atomic absorption spectrometry. Analytical Chemistry v.40, no, 11, pp. 1682-1686, California State Water Pollution Control Board. 1954. Report on the investigation of the travel of pollution, Pub. No, 11, Sacramento, California Ehrlich, G. G,, T. A. Bhlke, and J, Veechioli, 1972. Micro- bial aspects of groundwater recharge injection of purified chlorinated sewage effluent, U.S. Geological ‘Survey Professional paper 800-B. pp. B241-B245. Ehilich, G. G., H.F.H. Ku, J. Vecehioli, and T. A. Ehlke. 1977, Microbial effects of recharging the Magothy aquifer, Bay Park, New York, with certiary-treated sewage. U.S. Geological Survey Professional Paper 7SL-E. Karl, D, M. and P, A. LaRock. 1975. Adenosine triphos phate measurements in soil and marine sediments. J. Fish, Res. Bd, Can. v. 32, no, 5, pp. 599607. Lance, J. C. and F. D. Whisler. 1972. Nitrogen balance in soil columns intermittently flooded with secondary sewage effluent. J. of Environ, Qual. v, 1, no. 2, Pp. 180-186. Martens, C, $. and J. Van Klump, 1980. Biochemical cyeling in an organie-tich coastal marine basin. 1 Methane sediment—water exchange processes. Geochim, Cosmochim, Acta. v. 44, no. 3, pp. 471 490. Oberdorfer, J. A. 1983. Wastewater injection: near-well processes and their relationship to clogging. Pb.D. dissertation, University of Hawaii at Manoa, Honolua Oberdorfer, J. A. and F. L. Peterson. 1982. Wastewater injection well problems, processes and scandards. ‘Tech. Rep. No. 146, Water Resources Research Center, University of Hawaii at Manoa, Honolulu, Olsthoorn, T., N. 1982. The clogging of recharge wells, main subject. KIWA-communications 72, The Netherlands’ Testing and Rescarch Institute, Rijswijk, Netherlands. Peck, E. §,, A. L, Langhorst, and D. W. Obrien. 1979 Analysis of natural waters with an auromated induetively-couple plasma spectrometer system, Lawrence Livermore National Laboratory Report UCRL-81083, California, Petty, $. and F, L. Peterson, 1979, Hawaiian waste injection practices and problems. Tech. Rep. No. 123, Water Resources Research Center, University of Hawaii at Manoa, Honolulu, Ragone, §. E, 1977, Geochemical effects of recharging the Magothy aquifer, Bay Park, New York, with tertiary: treated sewage, U.S. Geological Survey Professional Paper 751-D. Rice, R. C, 1974. Soil clogging during infileration of secondary effluent. J. Water Polly. Control Fed v.46, pp. 708-716. Smith S, $., W.J. Kimmerer, E. A. Laws, R. B, Brock, and T. Walsh, 1981, Kaneohe Bay sewage diversion experiment: Perspectives on ecosystem responses £0 nutritional perturbation. Pac. Sci. v. 35, no. 4, pp. 279-395, Vecchioli, J. and H.F.H, Ku, 1972, Preliminary results of| injecting highly treated sewage effluent into a deep sand aquifer at Bay Park, New York. U.S. Geological Survey Professional Paper 751-4. Veechioli, J, H.F.H. Ku, and D. J. Sulam, 1980. Hydraulic ‘effects of recharging the Magothy aquifer, Bay Park, New York, with tertiary-treated sewage. U.S, Geologi- cal Survey Professional Paper 751-F June A, Oberdorfer received a B.A. from Brown University in 1970, studied Geology at the University of Stockholm, Sweden in 1976-77, and received a Pb.D. in Hydrogeology from the University of Hawaii in 1983, She presently is Assistant Professor of Hydrogeology at San Jose State University, California. Frank L. Peterson received a B.A. in Geology from Cornell University in 1963, and an M.S. in 1965 and a Pb.D. in 1967 from Stanford University in Geology/ Hydrology. Since 1967 be bas been on the faculty of the University of Hawaii in Honolulu where be presently is Professor of Hydrogeology and Chairman of the Depart- ment of Geology and Geophysics, and Researcher with the Hawaii Water Resources Research Center. 761