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.     

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.     

Seasonal variation of phosphorus release from the sediments of Shallow Lake Balaton (Hungary)

Phosphorus release was low from intact sediment cores of the mesotrophic area of the lake throughout the year, and amounted to 0.3 mg P m⁻² day⁻¹ during autumn in short-term incubations. In the hypertrophic area maximum release (2.8 mg Pm⁻² day⁻¹) was measured during summer.

Phosphorus release showed a rapid increase from long-term incubated intact sediment cores with the increasing pH of the overlying water. At the ecologically real maximum pH the release may amount to 0.8 and 4.0 mg P m⁻² day⁻¹ in the mesotrophic and hypertrophic areas, respectively. A release of 2.0–3.9 mg P m⁻² day⁻¹ was estimated from sediment suspensions of the hypertrophic area within a pH range of 8–9. These values are similar to the external phosphorus loadings of the respective areas.

The most important phosphorus mobilizing factors are pH and the decomposition of the organic matter in the sediments. Redox conditions may play a significant indirect role in the regulation of the internal loading.

A positive feedback is hypothesized between the internal phosphorus loading and primary production both processes being affected by the external loading in different ways.     

Growth of Selenastrum capricornutum in natural waters augmented with detergent products in wastewaters

A determination of whether the removal of phosphate builders from detergents would modify the ability of domestic secondary treated sewage effluent to stimulate the growth of a test alga (Selenastrum capricornutum-Printz) in receiving waters alone and augmented with detergent products was made. The lakes used as sources of test waters were located in northeastern New York State and possessed total phosphorus concentrations ranging from ca. 0.01 to 0.04 mg P1⁻¹.

The alga experienced stimulation in all three test lake waters from secondary sewage containing detergent with phosphate or detergent without phosphate. A concentration of 60 μg P 1⁻¹ was sufficient to effect significant algal growth in two of the test waters; however, concentrations ranging up to 110 μg P 1⁻¹ did not generate such a response in the third test water. This latter result and others suggested that neither phosphorus nor other nutrients from these wastewater additions were the factors fully accountable for the observed response(s).     

Internal phosphorus loading in a shallow eutrophic lake

Internal loading of phosphorus has been implicated as a major eutrophicating factor in Long Lake, Washington (Kitsap County). As a result of such loading, summer total phosphorus concentrations approach or exceed 100 μgP l⁻¹. Most of the summer loading of phosphorus is thought to have been released directly from the rich, flocculent sediment in the mid and northern part of the lake as a result of high pH (up to 10) related to phytoplankton photosynthesis. The lake also supports a dense submersed macrophyte crop (areal weighted mean dry weight of about 220 g m⁻²) composed primarily of Elodea densa. Although excretion of phosphorus from healthy E. densa was found to be minimal, the potential contribution of P indirectly from sediment via macrophyte uptake and subsequent decomposition in the winter was on the order of 200–400 kg yr⁻¹ or about 25–50% of the external loading. Nevertheless, loading of phosphorus during predrawdown summers is thought to have originated largely as a direct release from sediment due to high pH. Estimates of sediment phosphorus release determined from laboratory experiments, mass balance and core analyses ranged from 2.2 to 5.6 mg m⁻² day⁻¹.As a component of the restoration program, the lake (mean depth of 2 m) was drawn down nearly 2 m for 4 months during the summer and fall of 1979. The lake's trophic status was expected to improve due to sediment consolidation and/or macrophyte reduction. The drawdown resulted in an 84% reduction in macrophyte biomass in 1980 but minimal sediment consolidation (0.1 m). Winter decomposition of the much smaller macrophyte crop, apparently provided insufficient phosphorus in the spring to stimulate phytoplankton and to enrich midlake sediments, which has probably occurred in previous years. Low water column pH during the postdrawndown summer of 1980 resulted from relatively low rates of plankton photosynthesis. During the summer of 1980 internal loading of phosphorus was reduced and total phosphorus remained below 50 μg l⁻¹.     

Removal of saxitoxins from drinking water by granular activated carbon, ozone and hydrogen peroxide--implications for compliance with the Australian drinking water guidelines

In a laboratory-scale trial, we studied the removal of saxitoxins from water by ozone, granular activated carbon (GAC) and H₂O₂, and considered the implications of residual toxicity for compliance with the Australian drinking water standards. Cell-free extracts of Anabaena circinalis were added to raw, untreated drinking water obtained from a water supply reservoir to provide a toxicity of 30 μg (STX equivalents) l⁻¹. Ozone alone, or in combination with H₂O₂, failed to destroy the highly toxic STX and GTX-2/3, and only partially destroyed dc-STX, and the low-toxicity C-toxins and GTX-5. In all cases, the toxicity of the water was reduced by less than 10%. GAC removed all of the STX, dc-STX and GTXs, but only partially removed the C-toxins. However, the residual toxicity was reduced to the suggested Australian drinking water guideline concentration of 3 μg (STX equivalents) l⁻¹ without O₃ pre-treatment. Modelling the spontaneous chemical degradation of residual C-toxins following treatment shows that residual toxicity could increase to 10 μg l⁻¹ after 11 d due to formation of dc-GTXs and would then gradually decay. In all, residual toxicity would exceed the Australian drinking water guideline concentration for a total of 50 d.     

Interstitial inorganic phosphorus concentrations in lakes Mendota and Wingra

Interstitial P levels in Lake Mendota and Lake Wingra were evaluated as a function of season and water column and sediment depth. Interstitial water was obtained by the centrifugation-filtration method. Temporal variations were observed over the entire 15 cm sediment depth interval examined in all four locations evaluated. Interstitial reactive P (IRP) levels in Lake Mendota ranged from 0.014–1.67 mg l⁻¹ at the 5–6 m water column depth and from 1.20–5.75 mg l⁻¹ at the 18–19.5 m depth. IRP levels in Lake Wingra ranged from 0.029–2.15 mg l⁻¹ at 3.5 m and from 0.191–3.96 mg l⁻¹ at 2 m. Variations in interstitial P were attributed to variations in oxidation state of Fe as influenced by oxygen transport and reduction rates.     

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.     

Lake restoration by dilution: Moses lake, Washington

Dilution water, low in macronutrients, was added to Moses Lake on three occasions in 1977 and once in 1978 during the spring-summer period. The addition resulted in reducing the annual average inflow concentration of phosphorus from about 130–140 μg l⁻¹ to 100 μg l⁻¹. The water exchange rate in Parker Horn, which is 8% of the lake volume, increased from about 1% day⁻¹ normally to 7 and 11% day⁻¹ for the May–September period in 1977 and 1978, respectively. Lake water was displaced at a predictable rate in the whole lake as well as the areas proximal to the input, as verified by specific conductance.Improvements in lake quality, compared to values from 1969–70, were rather good with greater reductions in algal biomass occurring than might have been expected to result from the less impressive reductions in total P content. Chlorophyll a decreased by about 60–80% and total P decreased by about 50–60%, depending on the area of the lake. However, Chl a averaged only 15 μg l⁻¹ during May–September 1978, while total P was rather high at 70–80 μg l⁻¹. The fraction of the phytoplankton composed by blue-green algae decreased from 96% in 1970 to 68% in 1977–78. The cause for the effect on biomass and species composition is unknown, but may be related to dilution of blue-green excretory products.A dilution water input of about 6 m³ s⁻¹ continuously during April–September would require 20% less total water and should provide adequate control of eutrophication in at least 30% of the lake volume proximal to the input and Parker Horn. That would provide an exchange rate of 5% day⁻¹ for Parker Horn and should achieve lake water residuals by midsummer of 50%. Two additional inputs to the lake are also proposed as two more phases in the restoration project.     

Effects of water sample preservation and storage on nitrogen and phosphorus determinations: implications for the use of automated sampling equipment

The effects of freezing, acidification, refrigeration and extended storage without refrigeration on measured concentrations of forms of nitrogen and phosphorus were assessed in water samples taken from polluted and unpolluted streams in dry and wet weather. Emphasis was placed on likely changes associated with the use of automatic samplers in field conditions. The response of measured nutrient concentrations to different preservation methods and to extended storage without preservation varied widely between samples. For polluted streams where nutrient concentrations were high (ammoniacal nitrogen >0.1 mg l⁻¹; oxidised nitrogen, total Kjeldahl nitrogen, total and filterable phosphorus >1 mg l⁻¹), there was generally little proportional change in nutrients other than ammoniacal nitrogen after up to 6 d of storage without preservation. Where nutrient concentrations were low, up to 90% of ammoniacal nitrogen, 50% of oxidised nitrogen, 84% of total Kjeldahl nitrogen and 67% of total phosphorus was lost after 6 d. If samples cannot be retrieved immediately, automatic samplers should be refrigerated where possible. Acidification is a suitable alternative for preservation of nitrogen. Samples for filterable phosphorus should be filtered as soon as possible after collection. In some circumstances, unpreserved samples may provide an acceptable level of accuracy for evaluation of broad temporal trends or estimation of nutrient loadings.     

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.     

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.     

Decolorization of an azo dye by unacclimated activated sludge under anaerobic conditions

Studies on the reductive decolorization of a complex azo dye, Reactive Red 3.1, were made as part of the development of a practical approach to better exploit the metabolic potential of biomass in wastewater treatment. Decolorization was achieved at low and variable rates by mixed microbial cultures under various environmental conditions, including low pH and high salt concentration. It was caused by reductive cleavage of the azo bond to yield two aromatic amines. More reliable and effective decolorization rates, of up to 20–30 mg l⁻¹ h⁻¹, were given by unadapted activated sludge, (6 g l⁻¹) incubated with 400 mg l⁻¹ of Reactive Red 3.1 under anaerobic conditions. Decolorization also occurred best in static conditions.     

Simultaneous determination of trace amounts of free cyanide and thiocyanate by a stopped-flow spectrophotometric method

Simultaneous determination of free cyanide and thiocyanate was investigated using a stopped-flow spectrophotometric method. 1,3-dimethylbarbituric acid/isonicotinic acid at pH 5.2 was used as the colour reagent for both cyanide and thiocyanate determinations. The absorption spectrum of the complex formed by cyanide and thiocyanate with the colour reagent has a maximum wavelength at 600 nm, giving a low detection limit of 0.5 μg l⁻¹ for cyanide and 1.5 μg l⁻¹ for thiocyanate. Two proposed processes — 1,3-dimethylbarbituric acid combined with formaldehyde masking cyanide and the ferric-thiocyanate methods — can simultaneously determine free and other simple forms of cyanide and thiocyanate existing at pH 5.2; comparison of results demonstrates that both approaches are in agreement. By taking into account the effect of temperature on colour development and by using the ratio of the regression slopes, one kind of standard solution (thiocyanate) can be used for both cyanide and thiocyanate calibration, thereby avoiding the need to use toxic cyanide standard solutions.     

Measuring maximum specific growth rate and half saturation coefficient for activated sludge systems using a freeze concentration technique

To measure the maximum specific growth rate (μ_max) and the half saturation coefficient (K_s), a simple respirometric technique was used, where differing volumes of concentrated wastewater were contacted with biomass in a respirometer and the response measured as a change in oxygen uptake rate (ΔOUR). The ΔOUR was then related to the growth rate, and a series of substrate concentration/growth rate relationships determined from which μ_max and K_s were calculated. A freeze concentration technique was developed to concentrate the wastewater. The concentration technique did not alter the response of the microorganisms to the wastewater. Maximum specific growth rates (μ_max) and half saturation coefficients (K_s) were found to vary between 1.3 and 1.9 d⁻¹ and 1.5 and 3.2 mg l⁻¹, respectively.     

Removal of As(III) and As(V) from water using a natural Fe and Mn enriched sample

The arsenic removal capacity of a natural oxide sample consisting basically of Mn-minerals (birnessite, cryptomelane, todorokite), and Fe-oxides (goethite, hematite), collected in the Iron Quadrangle mineral province in Minas Gerais, Brazil, has been investigated. As-spiked tap water and an As-rich mining effluent with As-concentrations from 100 μg L⁻¹ to 100 mg L⁻¹ were used for the experiments. Sorbent fractions of different particle sizes (<38 μm to 0.5 mm), including spherical material (diameter 2 mm), have been used. Batch and column experiments (pH values of 3.0, 5.5, and 8.5 for batch, and about pH 7.0 for column) demonstrated the high adsorption capacity of the material, with the sorption of As(III) being higher than that of As(V). At pH 3.0, the maximum uptake for As(V) and for As(III)-treated materials were 8.5 and 14.7 mg g⁻¹, respectively. The Mn-minerals promoted the oxidation of As(III) to As(V), for both sorbed and dissolved As-species. Column experiments with the cFeMn-c sample for an initial As-concentration of 100 μg L⁻¹ demonstrated a very efficient elimination of As(III), since the drinking water limit of 10 μg L⁻¹ was exceeded only after 7400 BV total throughput. The As-release from the loaded samples was below the limit established by the toxicity characteristic leaching procedure, thus making the spent material suitable for discharge in landfill deposits.     

Heavy metals in seawater: Effects on limpet pedal mucus production

Toxicological modification of molluscan mucus production has largely been ignored. This is probably due to an underestimation of the r le of mucus in molluscan physiology and its energetic cost. This paper reports that laboratory exposure to episodic doses of waterborne copper and zinc serve to reduce pedal mucus production by the common limpet Patella vulgata L. to about 60% of the unstressed rate. The metals are effective in this respect at concentrations as low as 10 μg l⁻¹, which in the case of zinc is below the current U.K. environmental quality standard. All metal doses reduced mucus production to the same level. This suggests a behavioural response of the limpet, limiting activity. The reduction in mucus production has important consequences both for limpet ecology and for the ways in which biological energy allocation and transformation are assessed.     

Development of an advanced biological treatment system applied to the removal of nitrogen and phosphorus using the sludge ceramics

To develop a method of forming lake sediment into sludge ceramics with porosity and good biological adhesion for use as a medium for microorganisms in wastewater treatment, a study of the effects of forming conditions was conducted by adjusting the water content of sludge and compounding some additives. By adjusting the water content of the raw material at the kneading/pelletizing step to 40–42% and adding 3% waste glass to the raw materials to make up for the lack of flux, a sludge ceramic with a density in terms of specific gravity of saturated surface dry aggregate of about 1400 kg m⁻³ was formed. In addition, to develop a small-scale wastewater treatment system capable of removing nitrogen and phosphorus, a sludge ceramic was applied as a medium for biological filtration. The results indicated that the BOD removal nitrification rate were superior to those of conventional ceramic media, reached at 95.3% and 87.4%, respectively. The introduction of iron electrolysis resulted in high treatment performance achieving BOD levels of 10 mg L⁻¹ or less, T-N of 10 mg L⁻¹ or less and T-P of 1 mg L⁻¹ or less.     

Ammonia oxidation in nitrosomonas at NH3 concentrations near km: Effects of pH and temperature

Nitrosomonas europaea from continuous pure cultures was incubated with 26.4 μ M NH₃(= 0.37 mg NH₃-N l⁻¹) at various NH₄⁺ concentrations, pH values and temperatures. Measured rates of nitrite formation were significantly influenced by pH. Likewise unexpectedly, the maximum ammonia oxidation rate occurred between pH 6.7 and 7.0. Temperature had an even stronger effect on the rate of ammonia oxidation than the availability of NH₃. It is concluded that the assumption of a strict dependence of the rate of ammonia oxidation on substrate concentration is an unjustified oversimplification. Among the mechanisms which could explain ammonium uptake and oxidation near or below pH 7.0, the formation of NO from HNO₂ is considered.     

Sulfide inhibition of the methanogenic activity of granular sludge at various pH-levels

The effect of sulfide on the formation of methane from acetate in granular sludge originating from a UASB reactor has been determined using a new batch anaerobic toxicity assay. The assay is based on measurement of the methane concentration in the closed head space of a serum bottle, thus allowing operation at constant pH and without loss of sulfide via off-gases.

Sulfide toxicity appeared to be correlated with the free hydrogen sulfide concentration in the pH range 6.4–7.2. However this correlation did not hold at pH = 7.8–8.0. Free hydrogen sulfide concentrations leading to 50% inhibition were 250 mgS l⁻¹ in the pH range 6.4–7.2 and 90 mgS l⁻¹ at pH = 7.8–8.0.

The high tolerance for sulfide toxicity exhibited by the granular sludge can probably be attributed to the existence of a pH gradient in the sludge granules leading to an increased internal pH.