Acclimation to and biodegradation of nitrilotriacetate (NTA) at trace concentrations in natural waters

Acclimation to and biodegradation of nitrilotriacetic acid (NTA), an organic builder used in synthetic laundry detergents as the sodium salt, was studied at trace concentrations (ppb) in several river waters. The river waters tested ranged from those where extensive NTA exposure via detergents had not occurred, to those where NTA exposure had been continuous for several years. In rivers not previously exposed to NTA, acclimation and degradation were observed at the lowest initial concentration tested, 5 μg 1⁻¹. Degradation of NTA after acclimation followed apparent first order kinetics, and half lives for NTA removal ranged from 7 to 138 h at initial NTA concentrations of 50 and 5 μg 1⁻¹, respectively. Degradation of NTA in water samples where prior NTA exposure had already occurred required no acclimation and was less variable than in unexposed rivers. First order rate constants varied only slightly over a 1000-fold initial concentration range (1–1000 μg 1⁻¹) and NTA half lives ranged from 7 to 17 h. In general, our results indicate that microflora present in natural waters can acclimate to and degrade NTA, even if exposed to only trace levels in laboratory experiments. However, rates of NTA biodegradation are more rapid and less variable in river waters where natural NTA exposure has already occurred.     

An automated procedure for the determination of phosphorus

Procedures for the determination of dissolved orthophosphate and total phosphorus in surface fresh waters (e.g. rivers. lakes and reservoirs) and organic wastes (e.g. domestic sewage. creamery effluents and the like) (particulate or dissolved) are described. Total phosphorus compounds are converted to orthophosphate by acid persulphate digestion. The digestion time is 3 h which goes to completion without any supervision. The method allows for a maximum of 36 samples. 2 blanks and 2 standards to be processed simultaneously. There is no pH adjustment required. Interference from silica and iron(III) up to 20 mg l⁻¹ is absent. Detection limits for the automated step involving orthophosphate are 1 μg 1⁻¹. Recovery and effectiveness of proposed procedures are excellent.     

Automated fluorometric method for determination of boron in waters, detergents and sewage effluents

An automated method for the determination of boron in natural waters, detergents and sewage effluents is described. The method is based on the reaction of 4'-chloro-2-hydroxy-4-methoxybenzophenone (CHMB) with boron to produce fluorescent species, in a 90% sulfuric acid medium. The method has been made specific to remove any interferences from all major and minor ions and other organic compounds normally present in water. The method is capable of measuring different chemical forms of boron such as boric acid, borax, sodium perborate and tetraphenyl boron. The method analyses 10 samples per hour, in the 5–100 μg 1⁻¹ boron range. The rate of sample analysis can be increased to 20 per hour at higher concentration ranges. The limit of detection is 1 μg 1⁻¹ boron.     

Utilisation de l''algue oocystis sp. pour le traitement tertiaire des eaux usées—I. Culture en vrac de cellules préalablement conditionnées en cyclostat

With the aim of developing an efficient and economic method for the tertiary treatment of wastewater, a two-phased culture system of Oocystis alga is presented. During the first phase, a unialgal strain grows in a cyclostat supplied with secondary effluents diluted to a low concentration (50 μM NH₄⁺, i.e. 0.7 mg N 1⁻¹) of inorganic ions. Once the equilibrium is reached (i.e. the cell population is conditioned and the nutrient concentration is zero), in a second phase, the starved cells are mixed with a secondary effluent which has a higher nutrient content (200–400 μM NH₄⁺, i.e., 2.8–5.6 mg N 1⁻¹). Ion depletion (NH₄⁺, NO₃^-, NO₂^- and PO₄^3-) follows specific kinetics; successive identifiable stages related to photoperiod lead to a complete stripping of nutrients. In addition to ion concentrations, pH and cell population were determined every 2 h during the experiment. Results and conclusions are presented.     

Effect of exposure time and copper concentration on reproduction of the fathead minnow (Pimephales Promelas)

Three concurrent studies were conducted to determine the chronic effect of prespawning exposure to various concentrations of copper on fathead minnow reproduction. Copper was introduced into the three exposure systems to give 6-, 3-, and 0-months exposure prior to spawning. Prespawning exposure time had no significant effect on reproduction. Number of eggs produced per female decreased, however, with increase in copper concentrations. Egg production at copper concentrations of 37μg 1⁻¹ and higher was significantly lower (P = 0.05) than in the control, but at concentrations of 24μg 1⁻¹ and lower it was not different. The maximum acceptable toxicant concentration (MATC) was estimated to be 32μg Cu 1⁻¹, which is 0.07 of the 96h LC₅₀. This application factor for copper is similar to those found in other studies.     

Uptake and release of phosphate by a pure culture of Acinetobacter calcoaceticus

Uptake and release of phosphate by a pure culture of Acinetobacter calcoaceticus were investigated under aerobic and anaerobic conditions. The total phosphorus content of this bacterium varied from 0.3 to 1.7 mmol g⁻¹ dry cells or from 0.93 to 5.3% of dry cell weight under various culture conditions. The log-phase cells accumulated polyphosphates of 0.33−0.64 mmol P g⁻¹ dry cells. ³¹P NMR spectra suggested that a portion of polyphosphates was likely bonded to some sort of structural components of the cell. A. calcoaceticus release phosphate linearly with time when transferred from aerobic to anaerobic conditions. The release rate was in the range of 5.9–14.7 × 10⁻³ mmol P g⁻¹ dry cells h⁻¹ and about 4–8% of cellular phosphorus was released during the initial 6 h. During the process of phosphate release acetate was not taken up by this bacterium.     

Modified amperometric membrane probes for determining free and total residual chlorine in saline cooling waters

Modifications have been made to a Delta Scientific model 82124 free available chlorine probe so that it can be used to determine either the free or the total residual chlorine in cooling waters at coastal and estuarine power stations. For measurements of free residual chlorine, the internal filling solution of the probe was changed for one containing potassium bromide at pH 4. When the sample solution was dosed with potassium bromide and pH 4 buffer, the probe had a linear response over the range 0.04–1.0 μg ml⁻¹ Cl₂ and errors caused by changes in salinity were negligible. Total standard deviations for the analysis of 1.0 and 0.1 μg ml⁻¹ Cl₂ solutions were 0.055 and 0.01 μg ml⁻¹ Cl₂ respectively. For measurements of total residual chlorine a potassium iodide solution at pH 4 was used as the probe's internal filling solution and the sample solution was dosed with potassium iodide and pH 4 buffer. The probe had a linear response over the range 0.02-0.5 μg ml⁻¹ Cl₂, with total standard deviations of 0.05 and 0.01 μg ml⁻¹ Cl₂ at concentrations of 0.5 and 0.1 μg ml⁻¹ Cl₂ respectively.     

Plant-scale phosphate removal experiments at the Balatonfüred sewage treatment plant

Operational parameters at the Balatonfüred sewage treatment plant and the technology of chemical phosphate removal on a plant-scale have been examined in a 3-week series of experiments. Aluminium sulphate and iron(II) sulphate have been used as precipitating agents. It was found that the addition of 30 mg 1⁻¹ aluminium gave 90 per cent removal of total phosphorus. The addition of 60 mg 1⁻¹ iron(II) gave 89 per cent removal of total phosphorus. The costs of these chemicals are 0·93 Ft m⁻³ for aluminium and 0·11 Ft m⁻³ for iron precipitants, resp. Thus the iron is significantly less expensive as a phosphorus precipitant.     

The effect of wastewater phosphorus removal on shagawa lake, Minnesota: phosphorus supplies, lake phosphorus and chlorophyll a

In early 1973, the phosphorus supply to Shagawa Lake, Minnesota, was reduced by about 80% when a tertiary wastewater treatment plant began operating. Significant reductions in total and soluble reactive phosphorus concentrations have occurred in the lake since that time. By 1976 the average (volume weighted over the entire lake) total and soluble reactive phosphorus concentrations had declined from about 51 and 21 μg l⁻¹ to about 30 and 4.5 μg l⁻¹, respectively, corresponding to 40 and 80% reductions. During 1975 and 1976, chlorophyll a (averaged over the top 5 m) had decreased to less than 50% of the pretreatment level during May-June but during July-August little change had occurred.

A phosphorus residence time model projected equilibrium total phosphorus concentrations of about 12 μg l⁻¹ within 1.5 years. The fact that this level was not reached is attributed to a feedback of phosphorus from the sediments, primarily during summer. This phenomenon has been incorporated into a modified total phosphorus mass balance model which projects the phosphorus pattern through 1976 quite accurately. The close fit of the modified mass balance model implies that the phosphorus supply from the sediments has not diminished since treatment since treatment began, and that further recovery of the lake will depend upon how long this feedback of phosphorus from the sediments continues.     

Toxicities of total and chelex-labile cadmium to salmon in solutions of natural water and diluted sewage with potentially different cadmium complexing capacities

The LC₅₀ for total Cd averaged 4.8 and 8.0 μg1⁻¹ in river water and 33% sewage-treatment-plant effluent (STPE), respectively, and for Chelex-labile Cd, 3.9 and 5.6 μg1⁻¹, respectively. The LC₅₀ values for total Cd were significantly (P < 0.05) different, indicating a reduction in toxicity of Cd in the presence of 33% STPE, presumably due to complexation of Cd²⁺. The similarity of LC₅₀ values for Chelex-labile Cd indicates that that fraction contained toxic species of Cd at approximately the same concentration(s) in both river water and 33% STPE; it is therefore considered a better measure of Cd toxicity than total Cd. Furthermore, mortality was correlated with the concentration of Chelex-labile Cd but not with that of Chelex-nonlabile Cd. Measurements of Cd²⁺-complexing capacity by the Chelex method indicated that toxicity was due, at least in part, to Cd²⁺. Values were less than those obtained by the ion-selective-electrode method; these indicated that toxicity was due only to complexed Cd. Values from both methods were uncorrelated with LC₅₀ values.     

Toxicity of chlorine to juvenile spot, Leiostomus Xanthurus

The sensitivity of juvenile spot, Leiostomus xanthurus, to total residual chlorine (TRC) in flowing sea-water was investigated. Incipient LC₅₀ bioassays, histopathology, avoidance tests and the combined effect of thermal stress and TRC were used to assess sensitivity.

Estimated incipient LC₅₀ values were 0.12 mg 1⁻¹ TRC at 10°C and 0.06 mg 1⁻¹ TRC at 15°C. Histological examination of spot used in the incipient LC₅₀ bioassay at 15°C and sacrificed while alive indicated pseudobranch and gill damage occurred in individuals exposed to a measured TRC concentration of 1.57 mg 1⁻¹. Spot exposed to lower concentrations of TRC, 0.02 0.06 mg 1⁻¹ at 15°C and sacrificed alive showed no consistent tissue damage.

Spot demonstrated temperature dependent avoidance responses to TRC. At 10°C, a concentration of 0.18 mg 1⁻¹ was required for significant (X²; P < 0.05) avoidance; at 15 and 20°C, spot showed significant avoidance of TRC concentrations as low as 0.05 mg 1⁻¹.

Simultaneous exposure of spot to thermal stress (5, 10 or 13°C above the acclimation temperature of 15°C) at measured TRC concentrations of 0.05 0.07 and 0.34–0.52 mg 1⁻¹ demonstrated a significant, (Z²) with Yates correction, P < 0.05) increase in sensitivity to TRC with increased temperature and exposure times for some of the groups tested.     

Phosphorous limitation in an arctic river biofilm—A whole ecosystem experiment

A fourth-order arctic river was experimentally enriched with phosphate (7.7 ± 7.0 μ g 1⁻¹) to determine the effect of such a loading (equivalent to a community of 10,000 people) upon the trophically important biofilm. The effect upon a light-grown biofilm (an autotrophic/heterotrophic assemblage) and a dark-grown biofilm (predominantly heterotrophic assemblage) was determined after 28 days of colonization. Seven attributes of the biofilms were monitored, 2 autotrophic indices, chlorophyll , [¹⁴C]HCO₃ incorporation into lipids and 5 heterotrophic indices; [¹⁴C]acetate incorporation into lipids, metabolic heat output, turn-over times of microbially labile glucose and glutamate and mineralization of microbially recalcitrant ring-labelled [¹⁴C]hydroxybenzoic acid. The findings showed that the addition of phosphorus resulted in a substantial stimulation of both autotrophic and heterotrophic processes suggesting that arctic rivers of this type would be liable to cultural eutrophication.     

Histological and toxicological responses of the mummichog, Fundulus Heteroclitus (L.) to combinations of levels of cadmium and dissolved oxygen in a freshwater

Impact of dissolved oxygen concentration (D.O.) on toxicity of cadmium to mummichogs in a freshwater medium and histological changes associated with exposure were determined. Levels of mortality were related to duration of exposure, cadmium concentration, and levels of dissolved oxygen. Median tolerance concentrations, at 96h, ranged upward from 1.3 to about 3.0 mg Cd 1⁻¹ at 2.3 and 8.5 mg DO 1⁻¹, respectively. Statistical analyses of mortality data showed factors examined were interdependent and that Cd × DO and Cd × time interactions were significant (P < 0.01). No histopathology was evident at 3 mg Cd 1⁻¹, although histopathology was evident in gills from fish exposed to 28 mg Cd 1⁻¹ for 6 1/2 h.

Responses of mummichogs to cadmium in freshwater are compared with results of a previous study involving exposure of the species to cadmium in seawater and with responses of freshwater fishes subjected to various heavy metals. Differences and similarities in patterns of response are discussed in terms of water balance.     

Productivity and nitrogen balance in large scale phytoplankton cultures

Biomass production and nitrogen balance was studied in 35,000 gal (133,000 1) phytoplankton cultures comprising the first stage in a tertiary sewage treatment-mariculture system. The diatom Phaeodactylum tricornutum persisted for most of the study. At secondary sewage effluent loadings sufficient to produce residual dissolved inorganic nitrogen concentrations above approximately 5 μg atoms l⁻¹, an N:C ratio (molar) of 0.17 was obtained and algal growth was not nutrient-limited. Biomass levels, and hence pond particulate carbon and nitrogen output, varied in response to solar irradiance and dilution rate, but not temperature. Mean winter and summer yields were approximately 1 and 5 g (83 and 417 mg atoms) C m⁻² d⁻¹ respectively. An inverse relationship existed between algal biomass concentration and dilution rate, such that in the late spring optimal pond yields occurred between 0.55 and 0.65 dilutions d⁻¹. Better than 95% dissolved total nitrogen removal was obtained. Net dissolved organic nitrogen production, that would offset dissolved inorganic nitrogen removal, did not occur. Pond particulate nitrogen output was usually less than dissolved total nitrogen removal. Probable explanations for this include (1) ammonia evolution to the atmosphere at high pond pH, (2) particulate nitrogen sedimentation, and (3) denitrification. Of these, the first is believed to be quantitatively the most significant.     

Hypolimnetic aeration and dissolved gas concentrations: Enclosure experiments

Two large circular enclosures, each containing approx. 550 m³ of water, 14 m deep, and open to the mud-water interface, were used to monitor the effects of hypolimnetic aeration. One enclosure was held as a control, the other aerated every 3 or 4 days for a period long enough (usually < 2 h) to maintain hypolimnetic O₂ levels at > 4 mg 1⁻¹. Nutrient additions (10 g of 90% H₃ PO₄ and 250 g NaNO₃ per week) to each enclosure were controlled from the commencement of the experiment (17 June 1980) until its completion (2 November 1981). Temperatures in both enclosures were identical. Hypolimnetic O₂ levels in the control fell to zero during both summers, but remained at > 4 mg 1⁻¹ in the aerated enclosure. Free N₂ concentrations in the hypolimnion of the aerated enclosure was higher than in the control. Concentrations of H₂S in the control hypolimnion increased to > 5 mg 1⁻¹ and concentrations of CH₄ increased to > 18 mg 1⁻¹. Both remained at or near zero in the aerated enclosure. Tests of aerator efficiency suggested that the full air-lift design that was employed had an average O₂ exchange efficiency of 42% which is higher than the values reported for most other designs.     

A planktonic Oscillatoria species from Mississippi catfish ponds that produces the off-flavor compound 2-methylisoborneol

A planktonic, gas-vacuolate Oscillatoria species was isolated from catfish ponds in Mississippi during an episode of off-flavor and high 2-methylisoborneol (MIB) levels. Volatile compounds from unialgal cultures were isolated using closed-loop stripping, liquid-liquid extraction, and analyzed by gas chromatography and mass spectroscopy. The organism produced MIB at 75–87 μg 1⁻¹ after 2–3 wk of incubation at 25°C. The alga was found in moderate to high numbers in three pond water samples with high MIB levels, and low numbers in two other samples with low MIB levels. The organism was not present (less than one organism/10 ml) in nine other samples characterized by a “woody” or “swampy” odor and no detectable MIB. This Oscillatoria strain is believed to be the first blue-green alga that produces MIB ever isolated from Mississippi catfish ponds, and may be a cause of the off-flavor problem associated with MIB in those systems.     

Sediment-water exchange in Lough Ennell with particular reference to phosphorus

The significance and evaluation of sediment phosphorus in the continuing eutropic conditions noted in Lough Ennell was assessed. A high positive correlation exists between the concentrations of total Fe, citrate dithionite bicarbonate (CDB) extractable Fe, organic content, total Al and a number of phosphorus fractions (total P, inorganic P, organic P, apatite P and CDB extractable P) for all samples recovered. A significant inverse correlation was noted between CaCO₃ and most of the other parameters measured whereas no correlations were found for Mn. The sediment adsorption capacity for orthophosphate was found to be about 450 μg P g⁻¹ sediment. Phosphate release from hypolimnetic anaerobic sediments was considered unimportant in the biological sense due to the lack of mobility of this nutrient to the photic zones. Bioavailable P in the littoral zones (assumed to be non-apatite inorganic phosphorus, NAIP) comprised 14.5 tonnes in the uppermost 2 cm sediment layer, which is about 2.5 times the average annual external total P load. Littoral zone sediments, which are normally aerobic, accounted for an internal areal loading of 134 mg P m⁻² yr⁻¹ which is equivalent to 17 and 30% of the average external total P and inorganic P loadings respectively. This internal loading is a major contributory factor in the continuing eutrophic status of the lake.     

Occurrence and behaviour of linear alkylbenzenesulphonates, nonylphenol, nonylphenol mono- and nonylphenol diethoxylates in sewage and sewage sludge treatment

The fluxes of linear alkylbenzenesulphonates (LAS), nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) through sewage and sludge treatment of 29 Swiss sewage treatment plants were investigated. Reversed-phase high-performance liquid chromatography (HPLC) was used to determine LAS. Normal-phase HPLC was employed to measure NP, NP1EO and NP2EO which are metabolites of the nonionic surfactants of the nonylphenol polyethoxylate type (NPnEO). Quantitative determinations were performed of raw sewage, primary and secondary effluents and of sewage sludge. Under normal conditions of sewage and sludge treatment, LAS were efficiently removed from the raw wastewater (> 99% w/w) and were partly transferred to the sewage sludge (15–20% w/w). About 50% (molar base) of NPnEO in the sewage were transformed to NP and accumulated in the digested sludge. Large variations existed among different sewage treatment plants. It was estimated that 1.0 g m⁻² y⁻¹ of LAS and 0.3 g m⁻² y⁻¹ of NP are applied with sewage sludge to Swiss soils.     

Complexation of copper in the effluent of a sewage treatment plant and an estimate of its influence on toxicity to coho salmon

Measurements by cupric ion electrode of the complexing capacity of the effluent from a sewage treatment plant (STPE) averaged 0.300 mg 1⁻¹. Of the complexed Cu 67% was due to compounds of 10,000 MW. Organic compounds removable by activated carbon composed 88% of the total organic carbon and were responsible for 87% of the complexation. Complexation of Cu²⁺ by STPE diminishes the toxicity from total Cu to juvenile coho salmon; the LC₅₀ was 0.164 mg 1⁻¹ for river water vs 0.286 mg 1⁻¹ for 40% STPE. The LC₅₀ of Cu²⁺ was approximately the same (0.017 vs 0.022 mg 1⁻¹) in both matrices; this species thus appears to play a toxic role. The mean survival time in diluted STPE with added Cu was inversely proportional to the Cu²⁺ concentration.     

Gas chromatography in water analysis—I organic profiles of water sources

A method has been developed and used extensively for the routine chromatographic scanning of water sources for trace organic compounds. The method involves solvent extraction of the water with dichloromethane, followed by analysis of the concentrated extract by gas chromatography on a glass SCOT capillary column with flame ionisation detection to yield a water profile. Over 600 extracts from rivers, canals, reservoirs and various stages of water treatment, collected between January 1979 and October 1980 as part of a potability study, were examined. The profiles were quantified using n-paraffin standards and a computerised data system. Components were detected at levels as low as 0.01 μg 1⁻¹ in the water samples.

A Kratos MS-30 double-beam mass spectrometer equipped with a DS-50 data system was used in conjunction with gas chromatography to identify chemical types in over 60 of the organic extracts. Components were generally identified at levels as low as 0.1 μg 1⁻¹ in the water samples. Many components did not give molecular ions and reference spectra were generally unavailable. In such cases, accurate mass measurement using the double-beam technique, which allowed the calculation of atomic compositions for fragment and molecular ions, was particularly valuable.