Dissolved organic matter and the dissipation of chlorine in estuarine water and seawater

Dissolved organic matter in estuarine water and seawater collected in the summers of 1980 and 1981 in the James River, Virginia and the mouth of Chesapeake Bay were separated into fractions according to their nominal molecular weights (NMW) by ultrafiltration. Estuarine waters contained higher concentrations of dissolved organic carbon (DOC). Among the fractions, between 66–89% of the DOC was found in the fraction with NMW below 10,000. Estuarine waters also had higher chlorine demands. At a dose of 5 mg l⁻¹, in 23 h, about 90% of the added chlorine disappeared in estuarine waters, whereas, in seawater, only 60–75% of the chlorine had dissipated. At least two-thirds of the chlorine demand occurred in the first 5 h. About 10–30% of the chlorine demand may be attributed to the fraction with NMW above 10,000. The remaining chlorine demand was distributed almost equally between the fractions with ranges of NMW of 1000–10,000 and below 1000. If reactivity is measured in terms of organic chlorine demand (ΔClo) per unit weight of DOC, the fractions with lower NMW (< 1000 and 1000–10,000) always had a higher reactivity towards chlorine. Between these two fractions, the one with NMW between 1000 and 10,000 exhibited higher reactivity more frequently. The highest reactivity found was 1.4 mg ΔClo mg⁻¹ DOC.     

Dissolved organic carbon of coal slurry transport water

The qualitative and quantitative occurrence and fate of dissolved organic carbon (DOC) leaching into coal slurry transport water was examined in laboratory-generated coal slurries and wastewaters from the Black Mesa coal slurry pipeline. Laboratory slurries were formulated for both western coals (Wyodak, Montana Rosebud and Black Mesa) and eastern coals (Illinois No. 6 and Pittsburgh No. 8). Sephadex G-25 elution profiles and ultrafiltration studies indicate that the majority of the organic compounds in western coal slurry wastewaters were lower (less than 1000) molecular weight species (62% for Wyodak and 74% for Montana Rosebud). Biochemical Oxygen Demand (BOD) for these particular wastewaters ranged from 50 to 150 mg l⁻¹ as determined through the use of an electrolytic respirometer. Also, there was a concomitant 51–74% reduction in the DOC levels in the wastewaters. This removal was primarily due to the removal of the lower (< 1000) molecular weight compounds by the seed inoculum. There was no evidence for the presence of mutagenic organics in the raw wastewater.     

Molecular weight distributions in activated sludge effluents

Bench scale activated sludge reactors with a solids retention time of 9 days were operated at all combinations of two levels of pH, dissolved oxygen (DO) concentration and feed type (pH 6 and 8; DO 1 and 7 mgl⁻¹; simple and complex feed). Long-term composite samples were collected and adjusted to neutral pH and equal concentrations of alkalinity and ammonia nitrogen. The molecular weight distributions of the soluble organic carbon (SOC) in the samples were determined by ultrafiltration through membranes with nominal rejection values of 1000, 10,000, 25,000 and 100,000. The distributions were generally bimodal with the bulk of the SOC in the largest and smallest fractions. Following ozonation to a residual of 0.30–0.35 mg 1⁻¹ after 5 min contact, the distributions were shifted so that more of the SOC appeared in the lowest molecular weight fraction although significant amounts remained in the other fractions. When samples were breakpoint chlorinated to a residual of 5–10 mg l⁻¹ free available chlorine after 2 h contact, very little high molecular weight material remained and almost all of the SOC appeared in the low molecular weight fraction. By using ³⁶Cl during breakpoint chlorination it was also possible to evaluate the distribution of organically bound chlorine among the molecular weight fractions and this revealed that the bulk of it was associated with organics having molecular weight less than 1000.     

Effect of pesticide concentration on the degradation process by combined solar photo-Fenton and biological treatment

The influence of pesticide concentration, expressed as dissolved organic carbon (DOC), on combined solar photo-Fenton and biological oxidation treatment was studied using wastewater containing a mixture of five commercial pesticides, Vydate, Metomur, Couraze, Ditumur and Scala. Two initial DOC concentrations, 200 mg L⁻¹ and 500 mg L⁻¹ were assayed. Variation in biodegradability with photocatalytic treatment intensity was tested using Pseudomonas putida. Thus the mineralisation required for combining with biodegradation of intermediates by activated sludge was 33% and 55% at 200 mg L⁻¹ and 500 mg L⁻¹, respectively. Biotreatment was carried out in a stirred tank in sequencing batch reactor (SBR) mode. As revealed by the biodegradation kinetics, intermediates generated at the higher pesticide concentration caused lower carbon removal rates in spite of the longer photo-Fenton treatment time applied. One strategy for treating water with high concentrations of pesticides and overcoming the low biodegradability of photo-Fenton intermediates is to mix it with a biodegradable carbon source before biological oxidation. This combination of photo-Fenton and acclimatized activated sludge in several SBR cycles led to complete biodegradation of a concentrated pesticide solution of 500 mg L⁻¹ DOC in 5 h with a carbon removal efficiency of 90%.     

Mechanism of NTA degradation by a bacterial mutant

Transport of nitrilotriacetic acid (NTA) into the cytoplasm of a bacterial mutant was an active process. The mutant was able to degrade NTA from an initial concentration of 290,000 μg l⁻¹ of NTA to less than 50 μg l⁻¹ in 45 min, representing a rate of 486 μg NTA degraded per hour per mg dry weight of cells. This extremely fast rate of NTA utilization was substantiated by kinetic studies in which a Km of 82 μg l⁻¹ and a V_max of 370 μg h⁻¹ (mg dry weight cells)⁻¹ were found. The maximal temperature for NTA degradation was 50°C. The ability of the mutant to metabolize NTA resided mainly in the cell membrane fraction. Exchange diffusion technique showed that glycine and acetic acid were the metabolic products of NTA degradation. No iminodiacetic acid (IDA), succinate or citrate could be detected.     

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.     

Addition of NaOH, limestone slurry and finegrained limestone to acidified lake water and the effects on smolts of atlantic salmon (Salmo salar L.)

A neutralization experiment comparing NaOH, limestone slurry and finegrained limestone was performed using smolts of Atlantic salmon as testfish. Smolts were raised on chronically acid Lake Liervatn (pH = 4.9–5.4, conductivity = 55 μ S cm⁻¹, Ca = 1.3 mg l⁻¹, labile Al = 40 μg l⁻¹). As a result testfish were sublethally stressed prior to the experiment, as indicated by low levels of plasma chloride. During the experiment, smolts were held in keepnets in the middle of large plastic enclosures without sediment contact. Rapid changes in pH and Al-speciation were recorded after addition of the neutralizing agents. No mortality of fish occurred during the 3 days exposure. Plasma chloride levels in fish exposed to limestone slurry, limestone and the lowest concentration of NaOH (pH = 5.9) did not differ significantly from levels in fish from the reference group. Fish exposed to the highest concentration of NaOH (pH > 7.45), however, experienced a significant decrease in plasma chloride levels. Increased sublethal stress in treatments with NaOH was presumably caused by the presence of aluminate ions [Al(OH)₄⁻] at high pH and by low concentrations of Ca. The importance of maintaining pH below 7 when using bases with monovalent cations is emphasized. Adding inorganic aluminium to the lake water induced loss of plasma chloride within 48 h at 70 μg labile Al l⁻¹ at pH 5.1 and 1.2 mgCa l⁻¹.     

Biodegradability of ozonation products as a function of COD and DOC elimination by the example of humic acids

Ozone pretreatment studies of humic acids were conducted to evaluate the effects of ozonation on the biodegradability of the oxidation products as a function of COD-, DOC-elimination, decrease of u.v.-absorbance and ozone consumption. A 50–60% decrease of the COD-value and a 30% decrease of the DOC-value lead to biodegradable products (BOD₅/COD = 0.4) in most cases independent of the pH-value and the initial concentration. To reach these results 3.4–4 mg ozone are consumed per mg initial DOC. With this ozone consumption complete decolorization of the solutions is achieved and the value of u.v./DOC decreases from 4 to 0.8 m² g⁻¹.     

Preliminary studies on the leaching of some trace metals from kitchen faucets

Preliminary studies were carried out on the leaching of copper, zinc, chromium, cadmium and lead from eight kitchen faucets by samples of raw, filtered and distributed Ottawa water, a sample of well water and deionized water containing 2 mg l⁻¹ aqueous fulvic acid. Leaching was effected by allowing the test solutions to stand in the inverted faucets for two successive 24-h periods. Concentrations of the metals found in the leachates were copper: first leaching, 0.12–28.0 mg l⁻¹, second leaching, 0.08-3.54 mg l⁻¹; zinc: first leaching, 0.13-10.25 mg l⁻¹, second leaching, 0.06-2.85 mg l⁻¹; chromium: first leaching, < 1.0 × 10⁻³ − 0.395 mg l⁻¹, second leaching, < 1.0 × 10⁻³−0.032 mg l⁻¹; cadmium: first leaching, < 0.05 × 10⁻³−0.01 mg l⁻¹, second leaching, < 0.05 × 10⁻³−4 × 10⁻³ mg l⁻¹; and lead: first leaching, < 0.2−110.0 mg l⁻¹, second leaching, < 0.2−82.0 mg l⁻¹. The faucets containing lead-soldered copper joints released high concentrations of lead, particularly in the case of leaching with the aqueous fulvic acid solution. Under the conditions of the present investigations it is indicated that in some cases the concentrations of metals leached could lead to intakes in excess of the maximum permissible limits for these metals. However, further investigations will be required to determine the possible contribution of these faucets to metal intake under normal usage.     

Comparative effectiveness of antifouling treatment regimes using chlorine or a slow-releasing bromine biocide

Five chlorine (Cl₂) and three slow-releasing bromine biocide [1-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH)] treatment regimes were compared under laboratory conditions to determine their effectiveness in controlling the fouling of 304L stainless steel heat exchanger tubing. The most effective Cl₂ treatments were low level (0.1 ppm or less) continuous applications. Three intermittent Cl₂ treatments (1 h day⁻¹ at 1.0 ppm, 1 h day⁻¹ at 0.5 ppm, and 3 × 20 min day⁻¹ at 0.5 ppm) were about equally effective. However, all three intermittent regimes were significantly less effective than the low level continuous treatments. The effectiveness of BCDMH treatment was similar to Cl₂ when used intermittently at similar residual concentrations as Cl₂ for 1 h day⁻¹ and continuously at low levels. These experiments indicated that low level continuous treatment was more effective than intermittent treatment for controlling biofouling.     

Effect of molybdenum and selenium addition on the denitrification of waste water

The involvement of molybdenum and selenium in enzyme systems responsible for dentrification has been cited by several investigators. In this investigation, a bench scale denitrification column was operated continuously at room temperature to study the effect of molybdenum, added singly or in combination with selenium, on nitrate reduction and COD utilization rates. Methanol was used as the sole source of carbon and electron donor. As expected both nitrate reduction and COD utilization rates increased significantly (P < 0.001) when molybdenum concentration in the feed reached 1.5 mg 1⁻¹ and the observed increase was maximum when molybdenum concentration was raised to 2.5 mg 1⁻¹. The rates could be increased further by incorporating 0.5 mg 1⁻¹ selenium in combination with 2.5 mg 1⁻¹ molybdenum. A possible biochemical interpretation of the observed stimulation is suggested.     

Caracterisation de la matiere organique dissoute presente dans les eaux en cours d'affinage: Influence des traitements appliques et du climat

Dissolved organic matter in treated surface waters (clarified, possibly ozonized, then GAC-filtered, Fig. 1), is fractionated by ultrafiltration into five molecular classes with MW < 300, 300–1000, 1000–5000, 5000–10000 or > 10,000. Dissolved organic carbon (DOC), oxidizability by KMnO₄ in hot alkaline medium and u.v. absorbances at 240, 254, 280, 300 nm are measured. Fourteen series of samples, distributed on an annual biological cycle are analysed (Figs 2 and 3); multivariate statistical analyses are performed.By PCA (principal component analysis), variations in water supplying the activated carbon units appear to depend for 47% on ozonation and temperature; but river flow rate and quantity of flocculant added are no longer responsible for such variations (Fig. 4). Three groups of water appear (Fig. 5), according to the applied ozone level (zero, medium, high); among the medium ozonized waters, the cold ones differ from temperate ones.Ozonation diminishes molecular size of compounds (Table 1): three major classes with MW < 5000 are present in non- or medium-ozonized waters, but only two, with MW < 1000, remain in highly ozonized waters. This treatment destroys MW > 10,000 and even 1000–5000 ones and yields MW < 300 products; it also minimizes u.v. absorbances and oxidizability. Seasonal variations occur in DOC content of medium ozonized waters, with maxima values in winter or spring and minima in summer or autumn (Fig. 6): occurrence of MW < 300 compounds follows that of DOC, but the presence of 5000–10000 ones is minimal in winter.Quality of GAC-filtered waters varies by 19% with temperature (Fig. 7); ozonation effects are minimized: only previously highly ozonized waters distinguished themselves from the others (Fig. 8). Waters, non or medium ozonized before GAC-filtration, are divided into cold, temperate and warm waters. One, two or three major classes of compounds with MW < 5000, remain in GAC-filtered waters, according to the ozone level applied previously. This filtration reduces DOC by 17%, decreases u.v. absorbances and oxidizability and gives water with the same 0.30 mg O₂ mg⁻¹ C ratio (Table 2): MW 1000–5000 class is much less oxidizable after ozonation-GAC filtration but, on the other hand, MW < 300 class appears rather less oxidizable without ozonation before biological filtration. DOC content in effluent follows that in influent (Fig. 9), but variations are less marked. Total efficiency of the filtration increases with temperature, but behaviour of compounds differs from one class to another: MW 300–1000 and 5000–10000 classes are the most affected; MW 1000–5000 is not really modified. Elimination of MW < 300 or 5000–10000 compounds depends on temperature and may be due to biological phenomena, a but that of 1000–5000 and > 10,000 classes, independent of this parameter, may be related to adsorption mechanisms.     

A comparison of the characteristics of soluble organic nitrogen in untreated and activated sludge treated wastewaters

Soluble organic materials containing nitrogen (SON) are present in effluents from activated sludge treatment of domestic wastewater, but little is known about the sources and characteristics of these materials. The objective of this research was to evaluate the characteristics of SON in untreated wastewaters and activated sludge effluents. Characterization techniques used included low microbial seed biodegradability, molecular weight distribution using gel filtration chromatography, removal by activated carbon and ion exchange, and analysis for free and combined amino acids. Activated sludge effluent SON was more refractory (40–50%; first-order decay rates for the remainder were about 0.014 day⁻¹ than SON in untreated wastewater (18–38%; decay rates for the remainder were 0.08–0.16 day⁻¹). SON produced biologically during treatment had decay rates (about 0.028 day⁻¹) similar to SON in municipal activated sludge effluents, and was from 20 to 100% refractory. Less than 10% of the SON in municipal activated sludge effluent consisted of free or combined amino acids. Approximately 15–30% appeared to nucleic acid degradation products. Fifty to 60% of the SON and SCOD had apparent molecular weights of less than 1800. Apparent molecular weight distributions of treated and untreated wastewaters were similar; however, the excess SON produced during activated sludge start-up contained considerably more SON with molecular weights greater than 1800. The 165–340 molecular weight fraction had a significantly higher SON to SCOD ratio than any other fraction for all wastewaters examined. Activated carbon adsorption efficiently removed SON (72 ± 9%) and SCOD (78 ± 6%) from treated and untreated wastewaters, and from biologically produced organics. Significantly more SON was removed by cationic exchange at pH 2.0 (33–56%) than by anionic exchange at pH 9.5 (10–24%) for all wastewaters tested. Cationic exchange at pH 2.0 selectively removed more biologically produced SON relative to SCOD.     

Toxicity of silver to rainbow trout (Salmo gairdneri)

The mean 96-h LC₅₀'s of silver with rainbow trout were 6.5 μg l⁻¹ and 13.0 μg l⁻¹ in soft water (approximately 26 mg l⁻¹ hardness as CaCO₃) and hard water (350 mg l⁻¹ hardness as CaCO₃), respectively. The long-term, “no effect” concentration for silver, added to the water as silver nitrate, was between 0.09 and 0.17 μg l⁻¹ after 18 months exposure in soft water. The “no effect” concentration is that concentration range which defines no observed effect. Based on mortalities different from the control, no mortalities attributable to silver occurred at 0.09 μg Ag l⁻¹, whereas 17.2% mortality occurred to fish exposed to 0.17 μg ll⁻¹. The “no effect” concentration does not reflect possible effects of silver on spawning behavior or reproduction, since female rainbow trout will not generally reach sexual maturity before 3 yr. At silver concentrations of 0.17 μg l⁻¹ or greater, silver caused premature hatching of eggs and reduced growth rate in fry. In one experiment, the eggs were completely hatched within 10 days of exposure; whereas, control eggs completed hatching after 42 days. The prematurely erupted fry were not well developed and frequently died. The growth rate of surviving fry was greatly reduced.     

An evaluation of the potential toxicity of treated bleached kraft mill effluent to striped bass (Morone saxatilis walbaum) larvae exposed through metamorphosis to the juvenile stage

Twenty-day-old striped bass (Morone saxatilis) larvae were exposed to a range of treated bleached kraft mill effluent (BKME) concentrations from 0 to 20% effluent by volume (v/v) under continuous flow test conditins. The experimental test concentrations in the 2–20% BKME test aquaria had a BOD₅ which ranged from < 1 to 5 mg l⁻¹, TSS 12–17 mg l⁻¹, and true color 35–416 mg l⁻¹. Bleached kraft mill effluent did not kill larvae exposed to it for 20 days through metamorphosis to the juvenile stage. The BKME did not alter growth in length, weight or condition factor in larvae over the 20-day exposure period as determined by multiple regression analysis. A linear regression analysis on the dry weight data at Day 20 only, however, indicated a trend of decreasing weight with increasing BKME concentration. Effluent-exposed larvae also developed normally during the 20-day study. All individuals examined completed the transformation from postlarvae to juveniles by the age of 40 days.     

Study of changes in concentration during penetration through the soil layers by means of co-relationship

This report presents a co-relationship method that is used to evaluate changes in water quality. The co-relationship based on the water quality in the Goto river basin, is defined as plots of concentration of dissolved matter against total residue on evaporation, the correlation coefficient and the regression equation. SiO₂ and COD concentrations in the water samples of the Goto river basin show a peculiar change that is independent of the total residue on evaporation and flow length, and this change is again found by means of the co-relationship. The peculiar change of SiO₂ is also observed in some rivers in Japan. The correlation coefficient of the total residue on evaporation and SiO₂ is about 0.2–0.6 in the Goto river basin and in some other rivers in Japan, and the intercept of the regression equation of SiO₂ and Cl⁻ is apt to show a plus value in SiO₂ but a minus value in Cl⁻ in most of the co-relationships. The plus value of the intercept and the gentle slope of SiO₂ show that SiO₂ concentration is independent from that of the total residue on evaporation, and the minus value of Cl⁻, shows that a certain value of total residue on evaporation corresponds to zero concentration of Cl⁻, which means Cl⁻ does not dissolve out from the soil colloid. Thus, the present report suggests that there is a peculiar behavior in some species in the water flow by means of the co-relationship.     

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.     

Adaptation of methanogenic sludge to high ammonia-nitrogen concentrations

The influence of ammonia-nitrogen concentrations in excess of 1500 mg 1⁻¹ on the methane formation from volatile fatty acids by two types of methanogenic sludge was investigated in batch experiments. One was digested sewage sludge, acclimated to 815 mg 1⁻¹ ammonia-nitrogen and the other was digested piggery manure, acclimated to an ammonia-nitrogen concentration of 2420 mg 1⁻¹. In the experiment with digested sewage sludge, methane formation took place still at an ammonia-nitrogen concentration as high as 5 g 1⁻¹. However, an increasing lag-phase was observed at increasing ammonia-nitrogen concentrations in the range 730–4990 mg 1⁻¹. On the other hand in digested piggery manure methane formation immediately started without any lag-phase in the ammonia-nitrogen concentration range of 605–3075 mg 1⁻¹. In the experiments with both types of sludge the maximum methane formation rate slowly decreased with increasing ammonia-nitrogen concentrations.     

An automated determination of low reactive phosphorus concentrations in natural waters in the presence of arsenic, silicon and mercuric chloride

An automated technique for reactive phosphorus, sensitive to <0.5 mg P m⁻³, is described. Interference from AsO³⁻₄-As and mercuric chloride is removed by thiosulphate in acid solution. The interference from 100 mg AsO³⁻₄-As m⁻³, 10 g m⁻³ molybdate-reactive silicon or 60 g m⁻³ mercuric chloride is equivalent to <0.5 mg P m⁻³.     

Conditions required for the precipitation of aluminium in acidic natural waters

Laboratory and field studies were carried out in order to define the conditions necessary for the precipitation of Al in natural waters of pH 4–6. It is concluded that if precipitation does occur it involves the formation of Al(oxy)hydroxide, not aluminosilicates or basic aluminium sulphates. The solubility product of the Al(oxy)hydroxide is highly temperature dependent (ΔH = −30.5 kcal⁻¹). It is also sensitive to concentrations of SO₄²⁻ and, more markedly, humic substances (HS); both of these decrease solubility, HS by more than an order of magnitude at a concentration of approx. 5 mg l⁻¹ (equivalent to approx. 2.5 mg l⁻¹ dissolved organic carbon). A semi-empirical equation is proposed that allows the prediction of the effective solubility product at different temperatures and at humic concentrations in the range 0–7 mg l⁻¹. Of the 113 natural water samples analysed, only one was calculated to be oversaturated with respect to Al(oxy)hydroxide.