Bjørn Olav Rosseland

The mixing zone between limed and acidic river waters : complex aluminium chemistry and extreme toxicity for salmonids

When liming running waters, dosers must compensate for different flow and water qualities and for the downstream inflow from acid tributaries which creates mixing zones. At a certain point in the mixing zone, a constant or fluctuating chemical disequilibrium will appear due to transformation processes. In laboratory assays, over-saturated solutions of aluminium with ongoing active precipitation of aluminium have been found to be especially toxic to fish. Recent experiments in a mixing zone in the limed River Audna, Norway, have confirmed this phenomenon. Atlantic salmon (Salmo salar L.) and sea trout (Salmo trutta L.) smolts were exposed to acid and limed waters and mixtures of the two waters downstream from the point of connection. In the acid tributary (mean values: pH=4.8, Ca=1.3 mg litre (-1)), Ali 236 microg litre(-1)=), LT5) was 22 and 40 h for Atlantic salmon and sea trout, respectively. In the mixing zone (pH=4.8-6.5, Ca=1.2-3.2 mg litre(-1), Ali=50-240 microg litre(-1)), LT50 was 7 h for both species, masking the normal species difference in tolerance. Osmoregulatory failure and rapid gill lesions occurred in the mixing zone as an effect of the transformation of Al into high molecular weight precipitating species. This is the first documentation of the existence of such highly toxic mixing zones in nature, and the results clearly show that the mixing zone is even more toxic to fish than acid aluminium-rich waters.

Response of zooplankton, benthos, and fish to acidification: An overview

This paper presents an overview of the response to acidification of aquatic fauna with special emphasis on Zooplankton, benthos, and fishes. Changes in behavior, body chemistry, reproduction, and species diversity are presented based on laboratory experiments and field studies in both Europe and North America. Differences in species sensitivity are discussed as they relate, not only to acidification but also to low calcium concentrations in the water, elevated aluminum concentrations, and presence of naturally occurring organic acids. The mechanisms—behavioral, physiological and ecological—enabling aquatic fauna to survive in acidified waters are discussed.

Mercury and Organochlorine Contamination in Brown Trout (Salmo Trutta) and Arctic Charr (Salvelinus Alpinus) from High Mountain Lakes in Europe and the Svalbard Archipelago

High concentration of Hg, less volatile PCB congeners and p,p′-DDE in Arctic charr from an arctic lake was mainly causedby biomagnification in the food chain where cannibalism was thedriving force. We suggest that low sediment fluxes of Hg, low net production of methyl mercury, and short food chains excludingpiscivory explain the low levels of Hg in the invertebrate feeding fish population in five European high mountain lakes.Concentrations of less volatile PCB congeners in insectivorous fish populations from the European high mountain lakes were mainly influenced by fish age and atmospheric deposition, indicated by the sediment inventory. Atmospheric deposition influenced by local sources may explain the higher concentrationsof pesticides (p,p′-DDT, p,p′-DDE and γ-HCH) observedin fish from the Pyrenees compared to the other sites. Theconcentrations of Hg and organochlorines did not exceedthe guidelines for fish consumption, except for Hg levelsin the oldest fish from the arctic lake.

Effects of hypo- and hyperoxia on transcription levels of five stress genes and the glutathione system in liver of Atlantic cod Gadus morhua

SUMMARY The transcript levels of three genes coding for antioxidants, Cu/Zn superoxide dismutase (SOD), catalase and phospholipid hydroperoxide glutathione peroxidase (GSH-Px), and those of two stress proteins, metallothionein (MT) and CYP1A, were examined with real-time quantitative (q) RT-PCR in hepatic tissue of Atlantic cod exposed to 46% (hypoxia), 76% (normoxia) and 145% (hyperoxia) O2 saturation (tank outlet). To evaluate the oxidative stress state, the levels of total glutathione (tGSH), reduced glutathione (GSH) and oxidized glutathione (GSSG) and subsequently the oxidative stress index (OSI), were determined in the same tissue samples. The transcript level of GSH-Px was significantly upregulated in fish exposed to hyperoxia, and significantly downregulated in fish exposed to hypoxia, compared to the normoxia group. Significant downregulation was also found for SOD and CYP1A transcriptional levels in fish exposed to hypoxia. The transcript levels of catalase and MT did not change in liver of cod exposed to suboptimal oxygen levels. No significant differences were seen between the groups for tGSH, GSH, GSSG or OSI. Prolonged exposure to unfavourable oxygen saturation levels did not alter the OSI, indicating that the antioxidant glutathione system is maintained at an unchanged level in liver of the examined cod.

Increased mortality of fish due to changing Al-chemistry of mixing zones between limed streams and acidic tributaries

The present study is mainly focusing on mortality variations of fish due to changing Alchemistry of mixing zones. An artificial mixing zone was made by pumping water from a limed stream and an acidic tributary into a mixing channel. Atlantic salmon (Salmo salar L.) parr were exposed to the mixed water, limed stream water, and acidic tributary water. Mortality, blood haematocrit and plasma Cl−-concentration were recorded. Neither mortality, nor changes in haematocrit and plasma Cl− were observed when fish were exposed to limed water, while in both acidic and mixed water, mortalities and loss of plasma Cl− were observed. The highest mortality rates were found within the initial part (0 to 20 s) of the mixing zone. Blood haematocrit increased only in fish exposed to acidic tributary water. Our results shows that changes in Al-chemistry and subsequent Al-polymerization occur when acidic tributary water is mixed with limed stream water. We have also demonstrated that the toxicity which can arise in mixing zones are greater than in the original acidic water before mixing. The variations in mortality observed are associated with the quality and quantity of Al-polymerization as well as ageing of the polymers.

Acute and sub-lethal effects in juvenile Atlantic salmon exposed to low μg/L concentrations of Ag nanoparticles

Silver nanoparticles (Ag-NP) are components in numerous commercial products and are discharged into the environment in quantities that are largely unknown. In the present study, juvenile Atlantic salmon were exposed to 1, 20, and 100 μg/L (48 h, static renewal) of a commercially available Ag-NP colloidal suspension in natural (soft) lake water. A solution of AgNO(3) containing 20 μg/L Ag(I) ions was also included to discriminate the effect of NPs from that of ionic silver. Furthermore, the commercial Ag-NP suspension was compared to an in-house synthesised colloidal NP suspension prepared from AgNO(3) and NaBH(4) in citrate buffer. The size distribution of Ag in all exposure solutions was characterised by 0.22 μm filtration and 10 kDa hollow fibre cross-flow ultrafiltration in combination with ICP-MS. All exposures were characterised by a relatively high proportion of Ag-NP in the colloidal size fraction 3-220 nm. For assessment of biological effects, acute toxicity, gill histopathology, blood plasma parameters (Na, Cl, glucose, haemoglobin), and gene expression of a selection of gill biomarkers were measured. Results showed that the gills accumulated Ag in all exposure groups apart from the fish exposed to 1 μg/L Ag-NP. Accumulated Ag caused concentration-dependent response increases in general stress markers such as plasma glucose and gill gene expression of heat shock protein 70. Furthermore, induction of the metallothionein A gene indicated that Ag had been internalized in the gills, whereas a concentration-dependant inhibition of Na/K ATPase expression indicated impaired osmoregulation at as low as 20 μg/L concentrations of Ag-NP. The commercial Ag-NP suspension caused acute gill lamellae necrosis at high concentrations (100 μg/L), potentially giving rise to the substantial (73%) fish mortality at this concentration. The two different Ag-NP preparations gave comparable results for several endpoints measured, but differed in MT-A induction and mortality, thus emphasising the variation in effects that may arise from different Ag-NP preparations.

Speciation of lead, copper, zinc and antimony in water draining a shooting range—Time dependant metal accumulation and biomarker responses in brown trout (Salmo trutta L.)

The speciation of Pb, Cu, Zn and Sb in a shooting range run-off stream were studied during a period of 23 days. In addition, metal accumulation in gills and liver, red blood cell ALA-D activity, hepatic metallothionine (Cd/Zn-MT) and oxidative stress index (GSSG/ tGSH levels) in brown trout (Salmo trutta L.) exposed to the stream were investigated. Fish, contained in cages, were exposed and sampled after 0, 2, 4, 7, 9, 11 and 23 days of exposure. Trace metals in the water were fractionated in situ according to size (nominal molecular mass) and charge properties. During the experimental period an episode with higher runoff occurred resulting in increased levels of metals in the stream. Pb and Cu were mainly found as high molecular mass species, while Zn and Sb were mostly present as low molecular mass species. Pb, Cu and Sb accumulated on gills, in addition to Al origination from natural sources in the catchment. Pb, Cu and Sb were also detected at elevated concentration in the liver. Blood glucose and plasma Na and Cl levels were significantly altered during the exposure period, and are attributed to elevated concentrations of Pb, Cu and Al. A significant suppression of ALA-D was detected after 11 days. Significant differences were detected in Cd/Zn-MT and oxidative stress (tGSH/GSSG) responses at Day 4. For Pb the results show a clear link between the HMM (high molecular mass) positively charged Pb species, followed by accumulation on gills and liver and a suppression in ALA-D. Thus, high flow episodes can remobilise metals from the catchment, inducing stress to aquatic organisms.

Bioaccumulation of organochlorine pollutants in the fish community in Lake Årungen, Norway.

Organochlorine pollutants in the major fish species (pike Esox lucius, perch Perca fluviatilis, and roach Rutilus rutilus) of Lake Arungen, Norway, were investigated after an extensive removal of large pike in 2004. The organochlorine pollutants detected in fish liver samples in 2005 were dichlorodiphenyltrichloroethane (DDTs), polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), and heptachlor epoxide (HCE). DDTs were the dominant among all analyzed OCs. Sigma PCB and HCB, detected in fish from two clearly distinct trophic levels (prey and predators), give an indication of biomagnification. All OC concentrations in female pike were significantly lower compared to males, which might be due to the removal of high concentrations of pollutants in roe during spawning.

Acid reign '95? — Conference summary statement

H. RODHE Department of Meteorology, Stockholm University, S-10691 Stockholm, Sweden P. GRENNFELT Swedish Environmental Research Institute (IVL), P.O. Box 47086, S-40258 G6teborg, Sweden J. WISNIEWSKI Wisniewski and Associates Inc., 6862 McLean Province Circle, Falls Churc,~, Virginia 22043, USA c. ~Gm~N Swedish NGO Secretariat on Acid Rain, P.O, Box 245, S-40124 G6teborg, Sweden G. BENGTSSON Provincial Government, Liinsstyrelsen i GOteborgs och Bohus Liin, S-40340 GOteborg, Sweden K. JOHANSSON Swedish Environmental Protection Agency, S-10648 Stockholm, Sweden P. KAUPPI Finnish Forest Research Institute, Unioninkatu 40 A, FIN-O0171 HeIsinki, Finland V. KUCERA Swedish Corrosion Institute, Roslagsviigen t 01, House 25, S-10405 Stockholm, Sweden L. RASMUSSEN Danish Forest and Landscape Research Institute, Skovbrynet 16, DK-2800 Lyngby, Denmark

Time and Ph-Dependent Detoxification of Aluminum in Mixing Zones between Acid and Non-Acid Rivers

Liming detoxifies aluminum in a time-dependent process following the increase in pH. Transformation of Ali into non-reactive or colloidal forms of Al reduces toxicity. To investigate the effects of pH on the detoxification rate, Atlantic salmon (Salmo salar) parr were exposed in four identical channel-tank setups differing only in mixing ratio (30:70, 16:84 or 6:94) between acid (pH 5.6, total Ali 90 µg Al·L−1) and non-acid water (pH 6.3, total Ali 3 µg Al·L−1). Two channels had identical mixing ratio (30:70), but differed with respect to pH (6.0 or >6.4) due to addition of lime. Fish were exposed for 140 hrs. in waters aged from 1 minute and up to 4 hours after mixing. Ali decreased within minutes after mixing at pH 6.4. The detoxification process required hours at pH 6.0. Al accumulation onto fish gills and fish homeostasis was related to Ali. The data suggest that the detoxification process, and therefore the water body affected by ongoing polymerization, was strongly influenced by pH, where a pH target for liming set at pH 6.4 detoxified water faster than a pH target of pH 6.0.