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.     

The use of uric acid as a method of tracing domestic sewage discharges in riverine, estuarine and coastal water environments

The chemical tracking of sewage effluents discharged into fresh and saline waters presents difficulties, especially in estuaries. The main difficulty is caused by the dissolved constituents being used to monitor the effluent also occurring naturally at similar levels. Uric acid is present at significant levels in untreated sewage and is not normally found in unpolluted waters. Until now no suitable routine method has been available for uric acid estimation in fresh and saline waters at levels normally encountered in the environment. In this paper we describe a recently developed technique using high-performance liquid chromatography which estimates uric acid in both fresh and saline waters in the range 1–10,000 μg l⁻¹ with a precision (2σ) of ±20% at 2 μg l⁻¹, ±4% at 40 μg l⁻¹ and ±2% at 10 mg l⁻¹.     

Chlorophenols in surface waters of the Netherlands (1976–1977)

In this paper an analytical method is described for the capillary gas chromatographic determination, after derivatization, of 19 individual chlorophenols in surface water. The minimum detectable amounts are for monochlorophenols 2 μg l⁻¹, for dichlorophenols 0.05 μg l⁻¹, for trichlorophenols 0.02 μg l⁻¹ and for tetra- and pentachlorophenols 0.01 μg l⁻¹. The results of a monitoring program in the river Rhine and other Dutch surface waters with respect to these compounds are presented. The results cover the period January 1976–December 1977. 2,6-Dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol had the highest frequencies of occurrence in the river Rhine and its tributaries. Pentachlorophenol was found in the highest concentrations (up to 11 μg l⁻¹).     

Note on a rapid and sensitive method for the determination of anionic detergents in natural waters at the ppb level

A rapid and sensitive method for the determination of anionic detergents in natural waters is developed using atomic absorption spectrophotometry and his (ethylenediamine) copper(II) ion. The method is suitable for a concentration range of 0–50 μg1⁻¹ (ppb), but its applicability can be extended up to 15 μg ml⁻¹. The limit of detection is 0.3 μg l⁻¹.     

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.     

Acute toxicity and behavioral responses of coho salmon (Oncorhynchus kisutch) and shiner perch (Cymatogaster aggregata) to chlorine in heated sea-water

The acute toxicity and behavioral response to chlorinated and heated sea-water was determined for coho salmon smolts and 1–3 month old shiner perch. LC₅₀'s were determined for 7.5, 15, 30 and 60 min exposure times; 13, 16 and 20°C (Δt = 0, 3, 7°C) temperatures and total residual oxidant (TRO) concentrations ranging from 0.077 to 1.035 mg l⁻¹. The mean 60 min LC₅₀ for shiner perch was significantly reduced (P ≤ 0.05) from 308 μg l⁻¹ TRO at 13°C to 230 μg l⁻¹ TRO at 20°C. The 60 min LC₅₀ for coho salmon decreased from 208 μg l⁻¹ TRO at 13°C to 130 μg l⁻¹ at 20°C. The LC₅₀'s for coho salmon in chlorinated sea-water averaged 55% of those for shiner perch. The relationship between TRO concentration, exposure time, and percent survival in chlorinated sea-water at 13°C is presented for both species.A significant (P ≤ 0.01) avoidance threshold for coho salmon occurred at 2 μg l⁻¹ TRO and was reinforced with increasing temperature. A significant (P ≤ 0.01) avoidance threshold for shiner perch occurred at 175 μg l⁻¹ TRO, while a significant preference (P ≤ 0.05 or 0.01) response at 16°C and 20°C occurred at 10, 25, 50 and 100 μg l⁻¹ TRO. The ecological implications of the toxicity tests and the behavioral responses are discussed.     

Acute and chronic toxicity of lead to rainbow trout salmo gairdneri, in hard and soft water

Lead was found to be highly toxic to rainbow trout in both hard water (hardness 353 mg l⁻¹ as CaCO₃) and soft water (hardness 28 mg l⁻¹. Analytical results differ greatly with methods of analysis when measuring concentrations of lead in the two types of water. This is exemplified in LC50's and maximum acceptable toxicant concentrations (MATC's) obtained when reported as dissolved lead vs total lead added in hard water. Two static bioassays in hard water gave 96-h LC50's of 1.32 and 1.47 mg l⁻¹ dissolved lead vs total lead LC50's of 542 and 471 mg l⁻¹, respectively. In a flow-through bioassay in soft water a 96-h LC50 of 1.17 mg l⁻¹, expressed as either dissolved or total lead, was obtained. From chronic bioassays, MATC's of lead for rainbow trout in hard water were between 18.2 and 31.7 μg l⁻¹ dissolved lead vs 120–360 μg l⁻¹ total lead. In soft water, where exposure to lead was initiated at the eyed egg stage of development, the MATC was between 4.1 and 7.6 μg l⁻¹. With exposure to lead beginning after hatching and swim-up of fry, the MATC was between 7.2 and 14.6 μg l⁻¹. Therefore, fish were more sensitive to the effects of lead when exposed as eggs.     

Particulate and dissolved trace metals in Lake Ontario

Particulate metal concentrations in the nearshore waters of Lake Ontario have been determined to be 690 ng l⁻¹ for Cu; 40 ng l⁻¹ for Cd; 180 ng l⁻¹ for Ni; 1690 ng l⁻¹ for Zn; 2100 ng l⁻¹ for Mn; and 700 μg l⁻¹ for Fe. These values are considerably higher than the particulate metal concentrations in the offshore waters: 130, 8, 34, 230, 110, 260 and 9000 ng l⁻¹ for Cu, Cd, Ni, Zn, Pb, Mn and Fe respectively. In general, 50–80% of the Cu, 10–40% of the Ni, 20–60% of the Cd and >60% of the Pb in the lake water were bound to the suspended particulates. From the standing crop of the particulate metals and the estimated rates of their deposition on the lake bottom, the residence times of the particulate metals in the lake water column have been estimated to be about 0.5 yr. on the average. The suggestion is made that particulate organic matter may be an important vehicle for metal transport to the Lake Ontario sediments.     

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.     

Distribution of halomethanes in potable waters of Kuwait

The distribution of bromine containing trihalomethanes in the water distribution system of Kuwait has been studied. Total halomethanes in the drinking water averaged 25.6 ± 9.1 μg l⁻¹ with a maximum of 50.5 μg l⁻¹. Average concentrations (μg l⁻¹) of individual compounds were: CHBr₃, 13.6 ± 4.6; CHBr₂Cl, 8.8 ± 3.7; CHCl₂Br, 3.3 ± 1.5. Water from roof top storage tanks contained significantly less halomethanes than that from underground reservoirs.     

Toxicity of sodium selenite to rainbow trout fry

In a study designed to examine the long-term effects of inorganic selenium (IV) on early life stages of rainbow trout (Salmo gairdneri), survival was significantly reduced at selenium concentrations of 47 and 100 μg l⁻¹ after 90 days of exposure. Length and weight were significantly reduced after 90 days of exposure to 100 μg l⁻¹. Whole-body residues of selenium increased with increasing exposure concentrations but appeared to decline between 30 and 90 days of exposure. Analyses of trout backbone indicated little change in bone development with exposure to selenium (IV) with one exception; calcium concentrations were significantly decreased in fish exposed to 12 μg l⁻¹ of selenium. Results of our study indicates that a recommended safe level of 10 μg l⁻¹ for inorganic selenium would not significantly affect growth and survival of rainbow trout; however, concentrations of selenium near this level can reduce the levels of calcium in the backbones of trout.     

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.     

Environmental chemistry of copper in Lake Monona, Wisconsin

Lake Monona, located at Madison, Wisconsin, received over 1.5 × 10⁶ pounds of copper sulfate in the past 50 yr to control excessive algal growth. Dissolved copper on Lake Monona epilimnion is inversely related to pH which indicates possible control of dissolved copper by basic copper carbonate. Concentrations as high as about 4 μg Cu l⁻¹ were found in Lake Monona epilimnion, which also contains 3.3 me l⁻¹ (milliequivalents per liter) of alkalinity, mostly bicarbonate. Concentrations of dissolved copper were consistently lower (0.3 μg Cu l⁻¹) in the hypolimnion. Sulfide probably controls dissolved copper in the hypolimnion during anoxic conditions because of sulfide insolubility. Particulate copper concentrations of about 3 μg l⁻¹ increased slightly with depth. The highest concentrations of copper in Lake Monona sediments (650 mg kg⁻¹) were found approximately 60 cm below the current sediment surface. Surface sediments of Lake Monona contained approximately 250 mg Cu kg⁻¹ sediment dry weight.     

Mercury fluxes in a natural forested Amazonian catchment (Serra do Navio, Amapá State, Brazil)

Mercury (Hg total) fluxes were calculated for rainwater, throughfall and stream water in a small catchment located in the northeastern region of the Brazilian Amazon (Serra do Navio, Amapá State), whose upper part is covered by a natural rainforest and lower part was altered due to deforestation and activities related to manganese mining. The catchment area is 200 km from the nearest gold mining (garimpo). Minimum and maximum Hg concentrations were measured monthly from October 1996 to September 1997 and were 3.5–23.4 ng l⁻¹ for rainwater, 16.5–82.7 ng l⁻¹ for throughfall (March–August 1997) and 1.2–6.1 and 4.2–18.8 ng l⁻¹ for stream water, in natural and disturbed areas, respectively. In the natural area, the inputs were 18.2 μg m⁻² year⁻¹ in rainwater and 72 μg m⁻² year⁻¹ in throughfall. This enrichment was attributed to dry deposition. The stream output of 2.9 μg m⁻² year⁻¹ indicates that Hg is being recycled within the forest as other chemical species or is being retained by the soil system, as confirmed by the cumulative Hg burden in the 0–10 cm surface layer, which was 36 480 μg m⁻². When the disturbed area of the catchment was included, the stream output was 9.3 μg m⁻², clearly indicating the impact of the deforestation of the lower part of the basin on the release of mercury. The Hg burden in the disturbed area was 7560 μg m⁻² for the 0–10 cm surface layer.     

Chronic toxicity of water-borne and dietary lead to rainbow trout (Salmo Gairdneri) in lake Ontario water

Rainbow trout (Salmo gairdneri) exposed to lead in Lake Ontario water demonstrated a 21-day LC₅₀ of 2.4 mg l⁻¹ lead. At lead concentrations ranging from 3 to 120 μg l⁻¹, log₁₀ of lead concentrations in most tissues of exposed fish appeared linearily related to log₁₀ of lead concentrations in water. Highest concentrations occurred in opercular bone followed by gill and kidney. Lead accumulation by brain was not clearly demonstrated. Exposure to lead in water at concentrations as low as 13 μg l⁻¹ caused significant increases in red blood cell (RBC) numbers, decreases in RBC volumes, decreases in RBC cellular iron content and decreases in RBC δ-amino levulinic acid dehydratase activity. No changes were observed in hematocrit or whole blood iron content. The changes indicated increased erythropoiesis to compensate for inhibition of hemoglobin production and increased mortality of mature red blood cells. After 32 weeks exposure to 120 μg l⁻¹ lead in water, 30% of remaining fish exhibited black tails, an early indication of spinal deformities. Lead added to food was not available for lead uptake by fish. Lead content of fish exposed to dietary lead was not elevated above control levels and the majority of lead consumed could be accounted for in the faeces. Dietary lead may have slightly inhibited uptake of dietary iron.     

Cardiovascular-respiratory responses of rainbow trout (Salmo gairdneri) during chronic exposure to sublethal concentrations of cadmium

The effects of exposure to 3.6 and 6.4 μg l⁻¹ cadmium for periods up to 178 days on cardiac and ventilatory rates, hematocrit, hemoglobin concentration and erythrocyte adenosine triphosphate concentration in adult rainbow trout, Salmo gairdneri, were investigated. Except for slight transitory responses, 3.6 μg l⁻¹ cadmium had no effect on any of the cardiovascular/respiratory parameters. Significant increases in cardiac and ventilatory rates, blood hematocrit and hemoglobin were observed in fish exposed to 6.4 μg l⁻¹ Cd over the entire exposure period while erythrocyte ATP concentration declined during the last stages of exposure. Further experiments on the responses of fish exposed to 6.4 μg l⁻¹ Cd for 30 days demonstrated an impairment of oxygen transfer across the gill. The results are discussed in terms of possible gill impairment and hyperactivity as toxic responses to cadmium.     

The effects of phenol and some alkyl phenolics on batch anaerobic methanogenesis

Phenol and seven alkylphenols (o-, m- and p-cresol, 2.5-, 2.6-, 3.4- and 3,5-dimethylphenol) were added at various concentrations to aliquots of domestic anaerobic sludge in Hungate serum bottles and these were incubated at 37°C. The concentration of methane in the headspace gas was monitored to determine if the phenolics were fermented to methane or if they inhibited the anaerobic process. Only phenol and p-cresol were fermented to methane. At 500 mg l⁻¹ (but not at 300 mg l⁻¹) 2,5-, 3,4- and 3,5-dimethylphenol reduced the rate and the amount of methane produced. The cresols were inhibitory at 1000 mg l⁻¹ but not at 400 mg l⁻¹.In cultures supplemented with acetate and propionate (VOA), and in unsupplemented cultures, phenol at concentrations up to 500 mg l⁻¹ was fermented to methane. Between 800 and 1200 mg l⁻¹ phenol, methane production was neither enhanced nor inhibited relative to control cultures containing no phenol. Inhibition of methane production was evident when phenol was present at 2000 mg l⁻¹. Thus the methanogens are less susceptible to phenol inhibition than are the phenol-degrading acid formers. In similar experiments with p-cresol: enhanced methane production was observed at concentrations of 400 mg l⁻¹; no enhancement or inhibition was observed at 600 mg l⁻¹; and inhibition was noted when p-cresol was present at 1000 mg l⁻¹.     

Concentrations of heavy metals in small Norwegian lakes

As part of regional surveys of lakes in Norway the concentrations of Zn, Pb, Cu and Cd were measured in surface- and bottom-water samples collected from representative, small, pristine lakes (136 in southern Norway sampled in October 1974, 58 resampled in March 1975, and 77 in northern Norway sampled in March 1975). The lakes, a statistically representative sample of small lakes in Norway, were chosen such that their watersheds are undisturbed. Heavy-metal concentrations in these lakes thus reflect only natural inputs and anthropogenic inputs via the atmosphere.The generally low concentrations (Zn 0.5–12.0 μg l⁻¹; Pb 0–2.0 μg l⁻¹; Cu 0–2.0 μg l⁻¹; Cd 0.1-0.5 μg l⁻¹) measured in lakes in central and northern Norway provide estimates of natural “background” levels. These estimates may be too high because they include the global-scale deposition of heavy metals from the atmosphere which has increased as a result of industrial activities.Concentrations of Zn and Pb in lakes in southernmost and southeastern Norway lie above these “background” levels, apparently because of atmospheric deposition associated with the acidic precipitation that falls over southern Scandinavia. Increased heavy-metal concentrations in acid lakes may also be due to increased mobilization of metals due to acidification of soil- and surface-waters.     

Lake Sammamish response to wastewater diversion and increasing urban runoff

Lake Sammamish has shown a decrease in its mean annual concentration of phosphorus following diversion of about one third of the external loading in 1968. During 1971–1975 the P concentration averaged 27 μg l⁻¹, in contrast to the prediversion (1964–1966) concentration of 33 μg l⁻¹, and may be equilibrating near the predicted steady state concentration of 22 μg l⁻¹. Neither phytoplankton biomass or Secchi visibility has changed following diversion, however the blue green component of the phytoplankton decreased by nearly 50%. The failure of biomass and visibility to improve is probably a result of similar pre- and postdiversion winter spring epilimnetic P concentrations. The marked reduction in P since diversion occurred during and prior to fall overturn and may have represented a supply of P for later summer early fall blue green algal populations that declined after diversion.Runoff from a rapidly developing westside portion (18%) of the watershed is contributing substantially to P loading of the lake. Development to a density of about ten dwellings ha⁻¹ has increased loading possibly on the order of 14%. Future development of the eastside portion (26% of watershed) may increase loading by 20% and be equivalent to nearly one half of the P previously diverted in 1968.     

Anodic stripping voltammetric study of the lability of Cd, Pb, Cu ions sorbed on humic acid particles

The sorption of Cd, Pb and Cu by humic acid particles has been studied at μg l⁻¹ levels using A.S.V. on a Hg film electrode as the measuring technique. The variables examined included amount of solid present (0.01–0.2% w/v), initial metal ion concn (10–100 μg l⁻¹), systems pH (5.3, 6.35, 8.15) and base electrolyte composition. The calculated capacity for specific adsorption of the metal ions was a few mmol M²⁺ kg⁻¹, or less. The apparent lability of part of the sorbed material was examined by analysing the base solution before and after filtering, and by adding Chelex 100 particles to the suspension. Some sorbed Cd²⁺ was A.S.V. labile, another fraction transferred to the resin. The effect of solution reactions on uptake was studied by making the 1 M CH₃COONa base solution 0.2 M in a range of Na⁺ salts (8 different anions), or in carboxylic acid content (5 acids) or in compounds having S-type bonding groups. Formation of complex ions in solution altered the extent of metal ion uptake, and in the case of Cu A.S.V. peak size, shape and position were varied. It is suggested that natural waters containing suspended matter should be analysed by A.S.V. “as received”, as well as after filtration since response differences provide guidance in respect to the lability of sorbed ions.