Comparative effectiveness of chlorine and chlorine dioxide biocide regimes for biofouling control

The effectiveness of chlorine (Cl₂) and chlorine dioxide (ClO₂) in controlling biofouling of 304L stainless steel heat exchanger tubing was compared using an experimental trough system. Three combinations of dose and contact time were evaluated. Chlorination coupled with a dispersant was also tested. Three criteria were used to assess the degree of fouling; organic carbon and dry weight of the fouling material accumulated on metal specimens and the visual appearance of this material on the specimens. These parameters correlated well with one another and therefore, collectively provided an effective means of evaluating biocide efficacy.Metal specimens in all troughs receiving biocide treatment were much less fouled than those in the trough receiving no biocide. Continuous application of Cl₂ at about 0.15 ppm was more effective than four 15-min 1 ppm Cl₂ applications per day. Both of these treatment regimes were more effective than a dose of about 1 ppm for 1 h day⁻¹. Use of a dispersant in combination with Cl₂ showed no significant reduction in the amount of biofouling material accumulation, although a difference in the texture of this material was observed. Unlike the Cl₂ results, low-level continuous ClO₂ treatment at 0.15 ppm resulted in biofouling similar to that when 1 ppm of ClO₂ was used for 1 h day⁻¹. Overall, ClO₂ was significantly (P < 0.05) more effective in controlling biofouling than Cl₂.     

Comparison of chlorine and chlorine dioxide toxicity to fathead minnows and bluegill

The comparative toxicity of total residual chlorine (TRC) and chlorine dioxide (ClO₂) was evaluated by conducting 96 h flow-through bioassays with three types of fish. The fish were subjected to an intermittent exposure regime in which biocide residuals were present for approx. 2-h periods beginning at 0, 24, 48 and 72 h into the tests. These conditions simulated the antifouling procedure (1 h day⁻¹ biocide addition) used to control biofouling of nuclear reactor heat exchangers at the Savannah River Plant near Aiken, South Carolina. LC₅₀ values showed that ClO₂ was approx. 2–4 times more toxic than TRC to: (1) juvenile and 1-year-old fathead minnows (Pimphales promelas); and (2) young-of-the-year bluegill (Lepomis macrochirus).The TRC mean 96-h LC₅₀ values were: 0.08 mg l⁻¹ for juvenile fathead minnows, 0.35 mg l⁻¹ for adult fathead minnows and 0.44 mg l⁻¹ for young-of-the-year bluegills. The ClO₂ mean LC₅₀ values were: 0.02 mg l⁻¹ for juvenile fathead minnows, 0.17 mg l⁻¹ for adult fathead minnows and 0.15 mg l⁻¹ for young-of-the-year bluegills.     

The toxicity of chlorine to a common vascular aquatic plant

Myriophyllum spicatum was exposed to various chlorine concentrations on a continuous and intermittent basis in 96-h toxicity studies utilizing a proportional diluter. Continuous exposure to chlorine concentrations as low as 0.05 mg l⁻¹ total residual chlorine (TRC) depressed shoot and total plant dry weights approx. 30% relative to controls. Shoot length was depressed approx. 16% at this concentration. Chlorophyll a was depressed 25% at 0.1 mg l⁻¹ TRC. However, intermittent exposure of plants to chlorine for three 2-h periods daily for 96 h indicated an insensitivity to repeated short term chlorine exposure at all concentrations but 1.0 mg l⁻¹ TRC. These results indicate that high level chlorine discharges from waste water facilities and electric generating plants could be a contributing factor impacting nearby submerged aquatic vegetation.     

Nickel stimulation of anaerobic digestion

An acetate-enriched methanogenic culture was assayed for nutritional stimulation by nickel in combination with other inorganic and organic nutrients, i.e. iron, cobalt, yeast extract, riboflavin and vitamin B₁₂. Acetate was automatically maintained at 2–3 g l⁻¹ by a pH Stat system so that substrate was not limiting. In the absence of nickel, the specific acetate utilization rates were in the range of 2–4.6 g acetate g⁻¹ VSS day⁻¹. In the presence of nickel, this rate was as high as 10 and when both nickel and yeast extract were supplemented this rate temporarily increased to 12–15 g acetate g⁻¹ VSS day⁻¹ . The maximum acetate utilization rate was observed to be 51 g l⁻¹ day⁻¹ as compared to 3.3 g l⁻¹ day⁻¹ for conventional high-rate digestion. Daily phosphate additions were required to sustain these high acetate utilization rates. An acetate utilization rate of 20–30 g l⁻¹ day⁻¹ was maintained for over 25 days. Microscopic examination of the culture revealed a predominance of a sarcina whenever stimulation was noted.     

Treatment of low strength domestic wastewater using the anaerobic filter

A laboratory scale anaerobic filter packed with synthetic high surface area trickling filter media was used to treat a low strength domestic wastewater averaging 288 mg 1⁻¹ COD. The filter was operated for 60 days after reaching steady-state at 20, 25, 35°C at a loading rate of 0.02 lb COD ft⁻³ day⁻¹ and 24 h hydraulic retention time. Filter effluent BOD₅ averaged 38 mg 1⁻¹ providing an average removal rate of 79%, and effluent COD averaged 78 mg 1⁻¹, corresponding to a 73% removal rate. Removal efficiencies showed very little sensitivity to daily fluctuations in influent wastewater quality. The filter performance at 25 and 35°C was not significantly different, but BOD and TSS removal efficiency declined a: 20°C. Gas production averaged 0.027 ft⁻³ of gas per ft³ of influent wastewater, or 1.875 ft³ of gas per pound of influent COD. Gas composition averaged 30% nitrogen, 65% methane, and 5% carbon dioxide. Ammonia nitrogen and sulfides both increased during treatment. It is concluded that the anaerobic filter is a promising candidate for treatment of low strength wastewaters and that post treatment for sulfides and ammonia may be necessary.     

High-rate overland flow

Recommended loading rates for treating raw domestic wastewater by overland flow are 6.3–15 cm wk⁻¹. Information provided in the literature yields little insight regarding the upper range of hydraulic loading rates that could be effectively treated by overland flow. Therefore, field investigations were conducted to evaluate the performance of the overland flow system at overland flow rates from 0.95 m³ day⁻¹ m⁻¹ width of slope (13 cm wk⁻¹ to 4.15 m³ day⁻¹ m⁻¹ (57 cm wk⁻¹).Preliminary treated municipal wastewater was pumped to overland flow slopes, each approx. 3.7 m wide and 36.5 m long. The slope of each plot was 2.5%. The cover crop consisted of a mixture of ryegrass, bluegrass and fescue grass. The plots were operated for 2 years at six different hydraulic loading rates.Effluent BOD₅ concentration averages varied from 6 to 11 mg l⁻¹. The reduction of influent BOD₅ concentration ranged from 87 to 93%. Mean effluent suspended solids values were from 6 to 9 mg l⁻¹ with reductions of influent concentrations of 91–95%. Hydraulic application rate had little effect on percent BOD₅ or suspended solids removal.Total phosphorus reductions were minimal at all hydraulic application rates due to limited soil water contact.Ammonia concentration in the effluent ranged from 1 mg l⁻¹ NH₃-N at the 0.95 m³ day⁻¹ m⁻¹ (13 cm wk⁻¹) applied flow rate of 11.7 mg l⁻¹ NH₃-N at the 4.15 m³ day⁻¹ m⁻¹ (57 cm wk⁻¹) loading rate. Ammonia and nitrogen reductions decreased as the applied flow rate increased. Consequently, lower overland flow rates are necessary for nitrogen removal.The use of high-rate overland flow could potentially reduce the land necessary for this form of land application, if nutrient removal was not a local concern.     

Treatment of poultry manure wastewater using a rotating biological contactor

A pilot scale, six stage rotating biological contactor was used to evaluate the feasibility of this process for the stabilization of liquid animal manures. Total disc surface area was approx. 16.7 m². Treatment efficiencies were determined at various waste strengths and influent flow rates.With loading rates of 14.7–322 g m⁻² day⁻¹, the average COD reduction was 61%. With loading rates of 4.88-24.4 g m⁻² day⁻¹, the average BOD₅ reduction was 87%. Total nitrogen removal averaged approximately 30% for the entire study. Mixed liquor oxygen uptake rates were generally in excess of 80 mg 1⁻¹ h⁻¹.Clarified effluent was non-odorous and suitable to be reused for manure flushing or spray irrigation. Treatment was not sufficient to permit effluent discharge to surface waters.     

Ozonation of water containing chlorine or chloramines. Reaction products and kinetics

Ozone reacts with free aqueous chlorine when present as hypochlorite ion (OCl⁻) with a second order rate constant of 120 ± 15 M⁻¹ s⁻¹ at 20°C. About 77% of the chlorine reacts to produce Cl⁻ and 23% is oxidized to ClO⁻₃. No ClO⁻₄ is formed. Conversion of chlorine to monochloramine reduces the ozone reaction rate to 26 ± 4 M⁻¹ s⁻¹, independent of pH, NH₂Cl is transformed quantitatively to NO⁻₃ and Cl⁻ by O₃. Rate data for other chloramines are also presented. The direct reaction of ozone with chlorine accounts for a significant amount of the chlorine and ozone demand found when the two oxidants are used in combination under water works conditions.     

Reactions of chlorite with activated carbon and with vanillic acid and indan adsorbed on activated carbon

The reaction between chlorite (CIO₂) and vanillic acid, at pH 6.0 in the presence of granular activated carbon (GAC), yielded several reaction products identifiable by GC/MS; no products were found in the absence of GAC. Indan and C1O₂ or C1O₂ reacted in aqueous solution and gave similar products in the presence and absence of GAC. Carbon exposed to C1O₂⁻ appears to become capable of promoting hydroxylation, decarboxylation, ring cleavage and CO₂ addition reactions with vanillic acid.Chlorite in aqueous solution was reduced by GAC predominantly to Cl⁻. The capacity of one type of virgin GAC for C1O₂⁻ reduction to Cl⁻ was about 80–90 mg C1O₂⁻ g⁻¹ GAC before the rate of reaction was sharply reduced.     

Restoration of heavily polluted branches of the Shatt Al-Arab river, Iraq

In view of the desire to improve the water quality of the heavily polluted branches of the Shatt al-Arab River at the City of Basrah, it was proposed to maintain effective flushing as well as contracting sewerage system. The present study was conducted in order to examine the water quality of these branches in an attempt to evaluate the effectiveness of the proposed flushing system. It has been found that their waters contained very low levels of dissolved oxygen and relatively high amounts of both COD and BOD₅. The annual average water quality parameters for Basrah Branches were: dissolved oxygen 3.4 ppm; pH 7.67; hydrogen sulphide 1.4 ppm; ammonia 97 μg-at. N l⁻¹; COD 15.9 mg l⁻¹; BOD₅ 12.7 mg l⁻¹; dissolved silicates 202 μg-at. Si l⁻¹; dissolved reactive phosphate 13.4 μg-at. P-PO₄³⁻ l⁻¹; nitrate 10.4 μg-at. N-NO₃⁻ l⁻¹; nitrite 2.1 μg-at. N-NO₂⁻ l⁻¹ and chlorophyll-α 14.3 mg m⁻³. Based on our calculations, it has been concluded that the proposed system is effective, thus within a flushing cycle all of the above mentioned parameters will become within the acceptable values of the Shatt al-Arab water quality. Moreover, this system has no appreciable effect upon the water quality characteristics of the Shatt al-Arab River due to the fact that it discharges a high volume of water annually. However, It has been recommended to dredge the deposited sludge to a minimum depth of 50 cm.     

A mercury-free accelerated method for determining the chemical oxygen demand of large numbers of water samples by autoclaving them under pressure with acid-dichromate

In order to fulfill the objective of a water control program based on frequent sampling in several wastewater treatment plants, rivers and lakes a simplified method for measuring COD was developed. The procedure, in this article called the RR-method, includes: small sample and reagent volume; rapid addition of a mixture of all reagents to the sample; exclusion of mercury; autoclaving at 120°C for 1 h in flasks with fitted glass stoppers. To avoid dilution before analysis the method has been adapted for wastewater (I: 10–300 mg O₂ l⁻¹) and fresh water (II: 10–100 mg O₂ l⁻¹).Parallel analyses on different types of water samples according to Standard Methods showed that the yield by the RR-method was about 10% lower (Table 2). With water from the wastewater treatment plant at Uppsala (COD around 20 mg O₂ l⁻¹), the two methods gave an identical result. The somewhat lower yield was mostly due to decreased dichromate concentration and oxidation temperature. The lower oxidation potential made correction for chloride interference unnecessary below 1 g Cl⁻ l⁻¹ (Table 1).The RR-method also showed a good correlation to the values for KMnO₄-consumption. Parallel analyses of 318 samples from 14 wastewater receiving lakes gave the correlation coefficient r = +0.90 (Fig. 1).     

Self-purification constants for a Nigerian stream

By a simulation method, the reaeration (k₂) and biodegradation (k₁) constants for a shallow turbulent stream in Ibadan have been estimated at 11.45 day⁻¹ and 3.33 day⁻¹ respectively. The high F-factor (k₂/k₁) of 3.44 confirmed the fairly high self-purification capacity of the stream suggested by a comparison of the water quality of the polluted stream at several points downstream of the pollution source.     

Palm oil refinery wastes treatment

Effluent from the refining of crude palm oil was subjected to physical-chemical and biological treatment. An inclined corrugated parallel plates oil separator spaced at 25 mm was used with hydraulic loading rates of 0.2, 0.5 and 1 m³ m⁻²-h. 91% oil and grease removal could be achieved at 0.2 m³ m⁻²-h. Coagulation and flocculation carried out on batch samples after oil and grease separation revealed that with 100 mg l⁻¹ alum addition BOD was reduced from 3500 to 450 mg l⁻¹ and COD from 8600 to 750 mg l⁻¹ after 30 min settling. Higher doses of alum and doses of polyelectrolyte, activated carbon and sodium hypochloride did not yield significant additional reductions in BOD and COD. Batch dissolved air flotation (DAF) removed 90% of the suspended solids with 2.7% solids in the thickened sludge at an A/S ratio of 0.014. This method yielded the similar effluent quality as the inclined corrugated plates oil and grease separator. Field data from a DAF plant compare closely with data achieved in this study. Activated sludge treatment on the effluent from the oil separator yielded a BOD of 46 mg l⁻¹ with a loading rate of 0.3 g BOD (g MLVSS)⁻¹-day. Total dissolved solids (TDS) remained high and removal through coagulation and chemical oxidation brought the COD level down to around 180 mg l⁻¹. Biokinetic coefficients Y, k_dK and K₃ were found to be 0.85 g VSS (g BOD)⁻¹, 0.016 day⁻¹, 0.12 g BOD (g VSS)⁻¹-day and 510 mg l⁻¹ BOD respectively.     

Determination of phosphate in wastewaters by ion-exclusion chromatography with flow coulometric detection

Ion-exclusion chromatography of PO₄³⁻ in wastewaters has been investigated on a cation exchange resin in the H⁺-form. Phosphate ion was chromatographed by ion-exclusion as H₃PO₄ formed by cation exchange, and monitored with a flow coulometric detector based on the electrochemical reaction of H⁺ ion from H₃PO₄ and p-benzoquinone at a constant applied potential (+0.45 V vs Ag-AgI) or a conductometric detector. A reasonable separation of PO₄³ from strong acid anions (Cl⁻ SO₄²⁻ and NO₃⁻) and CO₃²⁻ as coexisting anions could be accomplished by isocratic elution with 60% (v/v) acetone-water. The calibration graph for PO₄³⁻ with the flow coulometric detector was linear over the concentration range 1–150 ppm (slope = 0.982), but not with the conductometric detector. The agreement of the analytical results of PO₄³⁻ between the ion-exclusion chromatography with the flow coulometric detector and the colorimetry (molybdenum-blue method) was excellent for some industrial wastewater and domestic sewage samples.     

Environmental assessment of a road site built with MSWI residue

A 23-year-old road built with MSWI residue (mix of fly and bottom ashes) was investigated through the environmental assessment of the residue, soils (adjacent to and underlying the road) and seepage waters. The pH and ANC_4.3 of the material indicate a low carbonation and a high alkaline stock. The material leaches few trace elements. The underlying road soil shows significant effects with respect to K and Na, attributable to the MSWI residue. Effects regarding Cd, Cr, Cu and Ni are observed, yet pollution thresholds are not exceeded. Compared to groundwater thresholds, the MSWI residue percolate is of poor to very poor quality (French reference system — FWQAS) in terms of pH, K, Na, Cl⁻, F⁻, As and Cu. It lies above the intervention values of the Dutch Soil Protection Act (DSPA) for Cu, Ni and Pb. Downstream, water from the road shoulder (W_Sdr) is of very poor quality with respect to Na and Cl⁻, and fair to poor quality regarding K. All other parameters comply with the best quality thresholds (FWQAS and DSPA). The high Cl⁻ concentration of W_Sdr would not fit for direct discharge in any watercourse. Toward a weakly-mineralised water, Cd and Cu would also be penalizing. The geometry of the road site creates penalizing conditions increasing the washing of the MSWI residue. The road structure does not cause downstream effect as regards trace elements, but effects exist for Cl⁻, Na and K. Opposite downstream effects are observed (Ca, Mg, Mn and SO₄²⁻) due to farming treatments and the nature of the local soil.     

Nitrogen removal in artificial wetlands

This report describes investigations which have demonstrated the exceptional utility of artificial wetlands for the removal of nitrate from secondary wastewater effluents at relatively high application rates. The artificial wetlands (14 in number) were plastic-lined excavations containing emergent vegetation growing in gravel. Without supplemental additions of carbon, total nitrogen removal efficiency was low ( 25%) in both vegetated and unvegetated beds. When methanol was added to supplement the carbon supply and stimulate bacterial denitrification, the removal efficiency was extremely high (95% removal of total nitrogen at a wastewater application rate of 16.8 cm day⁻¹). Since methanol is a relatively expensive form of carbon, we tested the feasibility of using plant biomass, mulched and applied to the surface of marsh beds, as an alternate source of carbon. At a wastewater application rate of 8.4 cm day⁻¹, the mean total nitrogen removal efficiency for the mulch-amended beds was 86%. When the application rate was higher (16.8 cm day⁻¹) the mean total nitrogen removal efficiency was lower, 60% in the mulch-amended beds.By using plant biomass as a substitute for methanol, the energy savings for a treatment facility serving a small community (3785 m³ day⁻¹ or 1 mgd) would amount to the equivalent of 731 day⁻¹ of methanol. As the cost of fossil fuel increases, energy cost will become a predominant factor in the selection of small (0.5–5 mgd) wastewater treatment systems. However, in many cases where natural wetlands are either geographically unavailable or protected from wastewater discharge by environmental, legal, or aesthetic restraints, artificial wetlands offer a viable alternative for energy-effective treatment of municipal and agricultural wastewater effluents.     

Effects of aluminum and pH on the early life stages of smallmouth bass (Micropterus dolomieui)

The sensitivity of smallmouth bass Micropterus dolomieui to acidified conditions was examined by exposing recently-hatched fish to pH levels ranging from 5.1 to 7.5 and aluminum concentrations ranging from 32 to 1000 μg l⁻¹. The range of pH and aluminum concentrations included those found in the northern part of the species' range. Acute bioassays (96 h) conducted at a pH of 5.1 and aluminum concentrations 180 μgl⁻¹ resulted in total mortality. The LC₅₀ calculated for this species was 130 μg l⁻¹. At pH values of 6.1 and 7.5, mortality was low ( 20%) regardless of aluminum concentrations. A 30-day chronic toxicity test was conducted at three pH levels (low 5.1, intermediate 5.5–5.7 and high 7.3), each with two aluminum concentrations (approx. 0 and 200 μg l⁻¹). Survival was significantly lower in the test at pH 5.1 with aluminum, and at pH 5.7 with aluminum treatments than in the other treatments. Fish in the pH 5.1 without aluminum treatment had intermediate survival, while fish exposed to pH 5.7 without aluminum, pH 7.3 without aluminum and pH 7.3 with aluminum had high, and similar, survival. Sublethal effects on fish exposed to low pH and aluminum included deformities, reduced activity and abnormal swimming behavior. We conclude that the sensitivity of smallmouth bass to low pH and aluminum concentrations corroborates field investigations linking acidification and aluminum mobilization with depletion of smallmouth bass populations.     

Development of mathematical models for the treatment of an industrial wastewater by means of biological rotating disc reactors

In this study the extension of the mathematical model proposed by Grieves to experimental results obtained in the treatment of an industrial wastewater is examined. The laboratory-scale unit consists of three stages with seven discs per stage.The following conclusions are drawn: (1) the Grieves's model (originally derived for glucose solutions) is reliable also for an industrial wastewater; (2) within the range of organic loading of 8.7–27.7 g BOD₅ day⁻¹ m⁻², the diffusion of the organic substrate, through the liquid film adhering to the biological film, is the controlling step of the BOD₅ removal kinetics only when the disc rotational speed n is less than 0.6 rev min⁻¹; (3) for higher values of n, as those adopted for full-scale plants, bio-disc apparatus can be designed, with good approximation, by means of the Monod's equation, by considering the bio-disc unit as an idealized perfect mixing activated sludge reactor, whose volume and activated sludge concentration are equal to the volume of the active biological film and organism concentration in the same film.     

The stabilization of “dissolved” iron in freshwaters

Laboratory experiments have been conducted to see what substances are capable of holding iron at a concentration of about 1 ppm in a “dissolved” form (i.e. will pass through a 0.45 μm pore size filter) in oxygenated water. The results show that reagents capable of doing this include humic and tannic acids, surfactants such as sodium dodecyl sulphate and sodium dodecylbenzene sulphonate, and the inorganic ions silicate and phosphate. In contrast, the synthetic polymer polyvinylpyrrollidone and the simple ions Cl⁻, HCO₃⁻, SO₄⁻ and NO₃⁻ showed no ability to stabilise iron. The efficiency of phosphate at keeping iron in the “dissolved” state was found to decrease in the presence of cations, particularly divalent ones, but increased with rise in water pH in the range 6–11.It seems unlikely that much of the stabilization observed for any of the reagents tested is due to their forming complexes with the iron. A much more likely explanation is that the substances for which positive results were obtained are able to stabilize fine colloidal iron particles and inhibit them from forming larger aggregates.     

Nitrate reduction by denitrifying bacteria in single and two stage continuous flow reactors

Denitrification by a mixed bacterial population of medium containing 1000 mg NO₃⁻-N1⁻¹ and acetate as carbon source was studied in batch, a single stage continuous flow stirred reactor (CFSTR) and a two stage CFSTR at 30°C. The optimum pH for denitrification, nitratase, nitrite reductase activities and growth was found to be 7.5 in batch culture. A single stage CFSTR growth limited by nitrate had an optimum denitrification rate of 0.13 mg NO₃⁻-N mg⁻¹ cells h at a residence time of 8 h. The experimentally observed carbon to nitrate ratio (mg CH₃ COO⁻-C mg⁻¹ NO₃⁻-N)was 1.7 for the dilution rates of 0.02–0.18 h⁻¹. For the second stage CFSTR, bacteria growing at the maximum rate of 0.25 h⁻¹ and not limited by nitrate had a denitrification rate of 0.24 mg NO₃⁻-N mg⁻¹ h. Dissolved oxygen (up to 9.5 mg 1⁻¹) did not effect denitrification rates in the second stage CFSTR. As the second stage CFSTR runs progressed extensive wall growth occurred and concurrently the output gas contained increasing quantities of nitrous oxide. A development from this study would be a two stage CFSTR with wall growth in the second stage which would make an efficient nitrate removal process.