Controlling toxic cyanobacteria: effects of dredging and phosphorus-binding clay on cyanobacteria and microcystins

Sediment dredging and Phoslock^® addition were applied individually and in combination in an enclosure experiment in a Dutch hypertrophic urban pond. These measures were applied to control eutrophication and reduce the risk of exposure to cyanobacterial toxins. Over the 58 days course of the experiment, cyanobacteria (predominantly Microcystis aeruginosa) gradually decreased until they dropped below the level of detection in the combined treated enclosures, they were reduced in dredged enclosures, but remained flourishing in controls and Phoslock^® treated enclosures. Cyanobacteria were, however, less abundant in the enclosures (medians chlorophyll-a 30-87 μg l⁻¹) than in the pond (median chlorophyll-a 162 μg l⁻¹), where also a thick surface scum covered one-third of the pond for many weeks.Soluble reactive phosphorus (SRP), total phosphorus and total nitrogen concentrations were significantly lower in the combined dredged and Phoslock^® treated enclosures than in controls. Median SRP concentrations were 24 μg P l⁻¹ in the combined treatment, 58 μg P l⁻¹ in dredged enclosures, and 90 μg P l⁻¹ in controls and 95 μg P l⁻¹ in Phoslock^® treated enclosures. Hence, the combined treatment was most effective in decreasing SRP and TP, and in lowering cyanobacterial biomass.Microcystin (MC) concentrations were analyzed by LC-MS/MS. MC concentrations and cyanobacterial biomass were positively correlated in all treatments. Mean MC concentrations in controls (71 μg l⁻¹), Phoslock^® treated enclosures (37 μg l⁻¹) and dredged enclosures (25 μg l⁻¹) exceeded the provisional guideline of 20 μg l⁻¹, whereas mean MC concentrations were 13 μg l⁻¹ in the combined treated enclosures. All samples contained the MC variants dmMC-RR, MC-RR, MC-YR, dmMC-LR and MC-LR; traces of MC-LY and nodularin were detected in few samples. The different treatments did not change the relative contribution of the variants to the MC pool; MC profiles in all treatments and the pond showed dominance of MC-RR followed by MC-LR. In the surface scum of the pond, total MC concentration was extremely high (64000 μg l⁻¹ or 1300 μg g⁻¹ DW), which poses a serious health hazard to children playing on the banks of the pond. Based on our results and pond characteristics, we propose combined sediment dredging and Phoslock^® addition, fish removal and strong reduction of duck feeding by the neighborhood as most promising measures controlling cyanobacterial hazards in this pond.     

Controlling eutrophication by combined bloom precipitation and sediment phosphorus inactivation

The hypothesis that the combination of the flocculent polyaluminium chloride (PAC) with the lanthanum-modified bentonite Phoslock^® (Flock & Lock) could sink effectively a water bloom of cyanobacteria and could shift a turbid, cyanobacteria infested lake to a clear water lake was tested in a controlled laboratory experiment and a whole lake experiment. In the laboratory, a relatively low dose of the flocculent PAC (2.2 and 4.4 mg Al l⁻¹) was insufficient to sediment positively buoyant cyanobacteria (Microcystis aeruginosa). Similarly, the lanthanum modified clay (dosed at 390 mg l⁻¹) was insufficient to sediment the positively buoyant cyanobacteria. However, the combination of PAC and Phoslock^® effectively sedimented cyanobacteria flocks. Likewise, a combined treatment of 2 tons PAC and 18 tons Phoslock^® in Lake Rauwbraken in April 2008 effectively sedimented a developing cyanobacteria bloom of Aphanizomenon flos-aquae. The average chlorophyll-a concentration in the two years prior to this Flock & Lock treatment was 19.5 (±36.5) μg l⁻¹, while it was as low as 3.7 (±4.5) μg l⁻¹ in the years following the treatment. The combined treatment effectively reduced the amount of total phosphorus (TP) in the water column from on average 169 (±126) μg P l⁻¹ before the application to 14 (±15) μg P l⁻¹ after the treatment. Based on mean summer chlorophyll-a and TP concentrations, the lake was shifted from a eutrophic/hypertrophic state to an oligo/mesotrophic state. From directly after treatment in April 2008 until and including 2013, Lake Rauwbraken remained in an oligo-mesotrophic clear water state with TP reduced to less than 10% of the pre-treatment. This result shows that eutrophication in relatively small, isolated, stratifying lakes can be restored by targeting both water column and sediment P using a combination of flocculent and solid phase P-sorbent.     

Lake responses following lanthanum-modified bentonite clay (Phoslock) application: An analysis of water column lanthanum data from 16 case study lakes

Phoslock^® is a lanthanum (La) modified bentonite clay that is being increasingly used as a geo-engineering tool for the control of legacy phosphorus (P) release from lake bed sediments to overlying waters. This study investigates the potential for negative ecological impacts from elevated La concentrations associated with the use of Phoslock^® across 16 case study lakes. Impact-recovery trajectories associated with total lanthanum (TLa) and filterable La (FLa) concentrations in surface and bottom waters were quantified over a period of up to 60 months following Phoslock^® application. Both surface and bottom water TLa and FLa concentrations were <0.001 mg L⁻¹ in all lakes prior to the application of Phoslock^®. The effects of Phoslock^® application were evident in the post-application maximum TLa and FLa concentrations reported for surface waters between 0.026 mg L⁻¹–2.30 mg L⁻¹ and 0.002 mg L⁻¹ to 0.14 mg L⁻¹, respectively. Results of generalised additive modelling indicated that recovery trajectories for TLa and FLa in surface and bottom waters in lakes were represented by 2nd order decay relationships, with time, and that recovery reached an end-point between 3 and 12 months post-application. Recovery in bottom water was slower (11–12 months) than surface waters (3–8 months), most probably as a result of variation in physicochemical conditions of the receiving waters and associated effects on product settling rates and processes relating to the disturbance of bed sediments. CHEAQS PRO modelling was also undertaken on 11 of the treated lakes in order to predict concentrations of La³⁺ ions and the potential for negative ecological impacts. This modelling indicated that the concentrations of La³⁺ ions will be very low (<0.0004 mg L⁻¹) in lakes of moderately low to high alkalinity (>0.8 mEq L⁻¹), but higher (up to 0.12 mg L⁻¹) in lakes characterised by very low alkalinity. The effects of elevated La³⁺ concentrations following Phoslock^® applications in lakes of very low alkalinity requires further evaluation. The implications for the use of Phoslock^® in eutrophication management are discussed.     

Biochemical stress response in tetradifon exposed Daphnia magna and its relationship to individual growth and reproduction

Environmental risk assessment of chemicals toxicity requires the use of costly and labor-intensive chronic data and short-term tests provide additional information. Energy budget is used by the animals for their growth, reproduction, and metabolism and it is reduced in case of toxic stress. Tetradifon acaricide is frequently used in the European Mediterranean region and it is implicated in aquatic environmental pollution. Previous studies showed that the EC₅₀-24 h of tetradifon on Daphnia magna was 8.92 mg/L. Based on that, D. magna were exposed to sublethal tetradifon concentrations of 0.10, 0.18, 0.22 and 0.44 mg/L for five days in order to investigate their effect on intermediate metabolism. Caloric content was determined as biomarker of tetradifon toxicity. Results were analyzed using one-way analysis of variance (ANOVA) and Duncan's significant difference test was used to find differences between groups (α was set at p = 0.05). Daphnids energy content decreased as tetradifon concentration increased. At 120-h caloric content was depleted > 51% at pesticide concentrations of 0.18 mg/L and higher. In order to determine a possible link between the 5-d test and the 21-d chronic test, animals under short-term test were exposed to the same pesticide concentrations known to cause adverse effects on reproduction, growth and survival. Results from the present study indicated a good correlation between the proposed 5-day test and daphnid energy budget. Comparison between both, caloric content results and the chronic effect values obtained using life-table studies, suggested a good fit between them. These studies can be used as earlier, predictive and useful tests with comparable results to the classic chronic ones. Our results indicate that caution must be done about the use of tetradifon in the aquatic environment.     

Effects of aluminum treatment on phosphorus, carbon, and nitrogen distribution in lake sediment: a 31P NMR study

The effects of aluminum (Al) treatment on sediment composition of carbon (C), nitrogen (N) and phosphorus (P) were investigated in sediment representing pre- and post-treatment years in the Danish Lake S?nderby. 31P NMR spectroscopy analysis of EDTA-NaOH extracts revealed six functional P groups. Direct effects of the Al treatment were reflected in the orthophosphate profile revealing increased amounts of Al-P in the sediment layers representing the post-treatment period, as well as changes in organic P groups due to precipitation of phytoplankton and bacteria at the time of Al addition. Furthermore, changes in phytoplankton community structure and lowered production due to the Al treatment resulted in decreased concentrations of sediment organic P groups and total C. Exponential regressions were used to describe the diagenesis of C, N, and P in the sediment. From these regressions, half-life degradation times and C, N, and P burial rates were determined.     

Disinfection by-product formation of natural organic matter surrogates and treatment by coagulation, MIEX and nanofiltration

Potentially the most effective means of controlling disinfection by-products (DBPs) is to remove precursors before disinfection. To understand relationships between physical properties, treatability and DBP formation, nine natural organic matter (NOM) surrogates were studied. Their DBP formation and removal by coagulation, MIEX^® anion exchange resin and two nanofiltration membranes was measured. Whereas treatability of NOM surrogates was explained in terms of their physicochemical properties, the same was not true of DBP formation. Hence it was not possible to selectively remove compounds which generate high amounts of DBPs. Instead, precursor removal strategies based upon empirical DBP formation potential testing are more apt. Under conditions simulating full-scale performance, MIEX^® did not offer improved performance over coagulation. A hydrophobic nanofiltration membrane proved successful for removing neutral, hydrophilic surrogates, and hence is also suitable for DBP precursors of this character.     

Influence of Asellus aquaticus on Escherichia coli, Klebsiella pneumoniae, Campylobacter jejuni and naturally occurring heterotrophic bacteria in drinking water

Water lice, Asellus aquaticus (isopoda), frequently occur in drinking water distribution systems where they are a nuisance to consumers and water utilities. Whether they are solely an aesthetic problem or also affect the microbial water quality is a matter of interest. We studied the influence of A. aquaticus on microbial water quality in non-chlorinated drinking water in controlled laboratory experiments. Pure cultures of the indicator organisms Escherichia coli and Klebsiella pneumoniae and the pathogen Campylobacter jejuni as well as naturally occurring heterotrophic drinking water bacteria (measured as heterotrophic plate counts, HPC) were investigated in microcosms at 7 °C, containing non-sterilised drinking water, drinking water sediment and A. aquaticus collected from a non-chlorinated ground water based drinking water supply system. Concentrations of E. coli, K. pneumoniae and C. jejuni decreased over time, following a first order decay with half lives of 5.3, 18.4 and 1.3 days, respectively. A. aquaticus did not affect survival of indicators and pathogens substantially whereas HPC were influenced by presence of dead A. aquaticus. Growth rates increased with an average of 48% for bacteria grown on R-2A agar and an average of 83% for bacteria grown on yeast extract agar when dead A. aquaticus were present compared to no and living A. aquaticus present. A. aquaticus associated E. coli, K. pneumoniae and C. jejuni were measured (up to 25 per living and 500 per dead A. aquaticus) and so were A. aquaticus associated heterotrophic bacteria (>1.8*10⁴ CFU per living and >6*10⁴ CFU per dead A. aquaticus). A. aquaticus did not serve as an optimised habitat that increased survival of indicators and pathogens, since A. aquaticus associated E. coli, K. pneumoniae and C. jejuni were only measured as long as the bacteria were also present in the water and sediment.     

Effect of cadmium, lead and arsenic on the oviposition, hatching and embryonic survival of Biomphalaria glabrata

Biomphalaria glabrata is a widespread freshwater gastropod mollusc. The easy aquaculture of these organisms allow its use as an accessible tool for contamination bioassays. B. glabrata showed marked metabolic responses when exposed to cadmium, lead and arsenic. Those responses could also affect the reproduction of the snails. Taking into account this hypothesis, B. glabrata were exposed for 96 h (acute laboratory bioassays) to different concentrations of cadmium (0.1, 0.05 and 0 mg/L), lead (0.5, 0.1, 0.05 and 0 mg/L) and arsenic (0.5, 0.1, 0.05 and 0 mg/L). Snails were removed from the aquaria while eggs were left in the same contaminant concentrations. The effect of the assayed toxicants on snail reproduction was registered as the alterations of the total number of laid eggs (TNLE), hatching time and embryonic survival.At 0.10 mg/L cadmium significantly decreased the TNLE (p < 0.05) and no embryos survived. The lowest assayed level (0.05 mg/L) of cadmium, delayed the hatching time twice when it was compared with the control group (p < 0.01).Lead decreased the TNLE at 0.5 mg/L level (p < 0.01). The other assayed doses (0.05 and 0.10 mg/L) also decreased embryonic survival significantly (p < 0.05 and p < 0.01 respectively) and extended twice the time to hatching (p < 0.01). The 0.50 mg/L level killed all embryos.Arsenic at all studied concentrations decreased the TNLE (p < 0.05) while the hatching time was increased by 50%. Embryo survival only decreased at the highest level (0.5 mg/L) of arsenic assayed.In summary, the acute exposure (96 h) to cadmium lead and arsenic, altered the reproduction of B. glabrata, modifying the TNLE, hatching time and embryonic survival.     

Trends of phosphorus, nitrogen and chlorophyll a concentrations in Finnish rivers and lakes in 1975–2000

During recent decades the amounts of nutrients discharged to Finnish surface waters have markedly decreased. This has been achieved by considerable investments in water protection, which were made mainly to improve municipal and industrial wastewater purification. We investigated whether these water protection measures have decreased phosphorus and nitrogen concentrations in Finnish rivers and lakes. In addition, possible trends in chlorophyll a concentrations in lakes were studied. The data consisted of a total of over 68 000 monitoring results of 22 rivers and 173 lakes (or sub-basins of lakes) with different types of catchment areas. The study period covered the years 1975–2000 and the non-parametric Kendall Tau b and Seasonal Kendall tests were applied for detecting trends. Decreasing nutrient concentration trends were typical in many lakes and rivers earlier polluted by municipal and industrial wastewaters. Increasing nutrient concentration trends were common in smaller rivers and lakes receiving diffuse loading from agriculture. The results show that the investments directed towards wastewater purification have effectively improved the quality of Finnish inland waters. However, no clear effects of decreasing non-point loading were found. Thus, more effective measures should be directed towards decreasing non-point source loading.     

Effects of nickel on daphnia magna during chronic exposure and alterations in the toxicity to generations pre-exposed to nickel

Daphnia magna was cultured at sublethal nickel concentrations. The mean life expectancy was significantly less when exposed to 40 ppb Ni. Statistically significant reductions of the number of offspring, maximum body length of adults and of neonates were caused by 80 ppb Ni. The length and brood size of primiparous animals were significantly less when exposed to 120 ppb Ni. The intrinsic rate of population growth (r) was inversely proportional to nickel concentrations. During seven successive generations exposed to 160 ppb Ni, both the mean life span and the length of primiparous animals decreased significantly with increasing time. The progeny of nickel pre-exposed generations exhibited no adaptation towards nickel except an altered reproduction pattern which induced an increase of r. After the transfer into nickel-free water, the progeny of nickel pre-exposed generations showed an increase of body length, mean life span, number of offspring, brood size and brood number as well as the maximum body length of neonates. However, the progeny of pre-exposed generations remained smaller than the progeny of an untreated generation.     

Influence of high gas production during thermophilic anaerobic digestion in pilot-scale and lab-scale reactors on survival of the thermotolerant pathogens Clostridium perfringens and Campylobacter jejuni in piggery wastewater

Safe reuse of animal wastes to capture energy and nutrients, through anaerobic digestion processes, is becoming an increasingly desirable solution to environmental pollution. Pathogen decay is the most important safety consideration and is in general, improved at elevated temperatures and longer hydraulic residence times. During routine sampling to assess pathogen decay in thermophilic digestion, an inversely proportional relationship between levels of Clostridium perfringens and gas production was observed. Further samples were collected from pilot-scale, bench-scale thermophilic reactors and batch scale vials to assess whether gas production (predominantly methane) could be a useful indicator of decay of the thermotolerant pathogens C. perfringens and Campylobacter jejuni. Pathogen levels did appear to be lower where gas production and levels of methanogens were higher. This was evident at each operating temperature (50, 57, 65 °C) in the pilot-scale thermophilic digesters, although higher temperatures also reduced the numbers of pathogens detected. When methane production was higher, either when feed rate was increased, or pH was lowered from 8.2 (piggery wastewater) to 6.5, lower numbers of pathogens were detected. Although a number of related factors are known to influence the amount and rate of methane production, it may be a useful indicator of the removal of the pathogens C. perfringens and C. jejuni.     

Effects of pollution on land snail abundance, size and diversity as resources for pied flycatcher, Ficedula hypoleuca

Passerine birds need extra calcium during their breeding for developing egg shells and proper growth of nestling skeleton. Land snails are an important calcium source for many passerines and human-induced changes in snail populations may pose a severe problem for breeding birds. We studied from the bird's viewpoint how air pollution affects the shell mass, abundance and diversity of land snail communities along a pollution gradient of a copper smelter. We sampled remnant snail shells from the nests of an insectivorous passerine, the pied flycatcher, Ficedula hypoleuca, to find out how the availability of land snails varies along the pollution gradient. The total snail shell mass increased towards the pollution source but declined abruptly in the vicinity of the smelter. This spatial variation in shell mass was evident also within a single snail species and could not be wholly explained by spatially varying snail numbers or species composition. Instead, the total shell mass was related to their shell size, individuals being largest at the moderately polluted areas. Smaller shell size suggests inferior growth of snails in the most heavily polluted area. Our study shows that pollution affects the diversity, abundance (available shell mass) and individual quality of land snails, posing reproductive problems for birds that rely on snails as calcium sources during breeding. There are probably both direct pollution-related (heavy metal and calcium levels) and indirect (habitat change) effects behind the observed changes in snail populations.     

Simultaneous determination of microcystin contaminations in various vertebrates (fish, turtle, duck and water bird) from a large eutrophic Chinese lake, Lake Taihu, with toxic Microcystis blooms

This is the first to conduct simultaneous determination of microcystin (MC) contaminations in multi-groups of vertebrates (fish, turtle, duck and water bird) from Lake Taihu with Microcystis blooms. MCs (-RR, -YR, -LR) in Microcystis scum was 328 μg g^− 1 DW. MCs reached 235 μg g^− 1 DW in intestinal contents of phytoplanktivorous silver carp, but never exceeded 0.1 μg g^− 1 DW in intestinal contents of other animals. The highest MC content in liver of fish was in Carassius auratus (150 ng g^− 1 DW), followed by silver carp and Culter ilishaeformis, whereas the lowest was in common carp (3 ng g^− 1 DW). In livers of turtle, duck and water bird, MC content ranged from 18 to 30 ng g^− 1 DW. High MC level was found in the gonad, egg yolk and egg white of Nycticorax nycticorax and Anas platyrhynchos, suggesting the potential effect of MCs on water bird and duck embryos. High MC contents were identified for the first time in the spleens of N. nycticorax and A. platyrhynchos (6.850 and 9.462 ng g^− 1 DW, respectively), indicating a different organotropism of MCs in birds. Lakes with deaths of turtles or water birds in the literatures had a considerably higher MC content in both cyanobacteria and wildlife than Lake Taihu, indicating that toxicity of cyanobacteria may determine accumulation level of MCs and consequently fates of aquatic wildlife.     

Impact of toxic cyanobacteria on gastropods and microcystin accumulation in a eutrophic lake (Grand-Lieu, France) with special reference to Physa (= Physella) acuta

Hepatotoxic microcystins (MCs) produced by cyanobacteria are known to accumulate in gastropods following grazing of toxic cyanobacteria and/or absorption of MCs dissolved in water, with adverse effects on life history traits demonstrated in the laboratory. In the field, such effects may vary depending on species, according to their relative sensitivity and ecology. The aims of this study were to i) establish how various intensities of MC-producing cyanobacteria proliferations alter the structure of gastropod community and ii) compare MC tissue concentration in gastropods in the field with those obtained in our previous laboratory experiments on the prosobranch Potamopyrgus antipodarum and the pulmonate Lymnaea stagnalis. We explored these questions through a one-year field study at three stations at Grand-Lieu Lake (France) affected by different intensities of cyanobacteria proliferations. A survey of the community structure and MC content of both cyanobacteria and gastropods was associated with a caging experiment involving P. antipodarum and L. stagnalis. In total, 2592 gastropods belonging to 7 prosobranch and 16 pulmonate species were collected. However, distribution among the stations was unequal with 62% vs 2% of gastropods sampled respectively at the stations with the lowest vs highest concentrations of MC. Irrespective of the station, pulmonates were always more diverse, more abundant and occurred at higher frequencies than prosobranchs. Only the pulmonate Physa acuta occurred at all stations, with abundance and MC tissue concentration (≤ 4.32 µg g DW^− 1) depending on the degrees of MC-producing cyanobacteria proliferations in the stations; therefore, P. acuta is proposed as a potential sentinel species. The caging experiment demonstrated a higher MC accumulation in L. stagnalis (≤ 0.36 µg g DW^− 1 for 71% of individuals) than in P. antipodarum (≤ 0.02 µg g DW^− 1 for 12%), corroborating previous laboratory observations. Results are discussed in terms of differential gastropod sensitivity and MC transfer through the food web.     

Effect of COD/SO4ratio and Fe(II) under the variable hydraulic retention time (HRT) on fermentative hydrogen production

The effect of chemical oxygen demand/sulfate (COD/SO₄²⁻) ratio on fermentative hydrogen production using enriched mixed microflora has been studied. The chemostat system maintained with a substrate (glucose) concentration of 15 g COD L⁻¹ exhibited stable H₂ production at inlet sulfate concentrations of 0-20 g L⁻¹ during 282 days. The tested COD/SO₄²⁻ ratios ranged from 150 to 0.75 (with control) at pH 5.5 with hydraulic retention time (HRT) of 24, 12 and 6 h. The hydrogen production at HRT 6 h and pH 5.5 was not influenced by decreasing the COD/SO₄²⁻ ratio from 150 to 15 (with control) followed by noticeable increase at COD/SO₄²⁻ ratios of 5 and 3, but it was slightly decreased when the COD/SO₄²⁻ ratio further decreased to 1.5 and 0.75. These results indicate that high sulfate concentrations (up to 20,000 mg L⁻¹) would not interfere with hydrogen production under the investigated experimental conditions. Maximum hydrogen production was 2.95, 4.60 and 9.40 L day⁻¹ with hydrogen yields of 2.0, 1.8 and 1.6 mol H₂ mol⁻¹ glucose at HRTs of 24, 12 and 6 h, respectively. The volatile fatty acid (VFA) fraction produced during the reaction was in the order of butyrate > acetate > ethanol > propionate in all experiments. Fluorescence In Situ Hybridization (FISH) analysis indicated the presence of Clostridium spp., Clostridium butyricum, Clostridium perfringens and Ruminococcus flavefaciens as hydrogen producing bacteria (HPB) and absence of sulfate reducing bacteria (SRB) in our study.     

Effects of zinc on molting and body weight of the estuarine crab Neohelice granulata (Brachyura: Varunidae)

The semiterrestrial burrowing crab Neohelice granulata is one of the main inhabitants of the supratidal and intertidal zones of brackish salt marshes, estuaries and coastal lagoons from South America's Atlantic littoral. A large population of this species spreads out Mar Chiquita coastal lagoon (in Argentina) and its corresponding wetlands, and is considered as a key species within this system.Since high values of dissolved heavy metals (including Zn) have been recently reported within Mar Chiquita coastal lagoon, with levels unusually higher than those from other coastal systems within Argentina, it has been explored that the existence of a risk of environmental conditions endanger these populations. So, juveniles of this estuarine crab were experimentally exposed to increasing concentrations of dissolved Zn (i.e., 0, 0.5 and 1 mg Zn²⁺ L^− 1) during six months, the time involved between two successive molts; in addition, both the size and weight reached after each molt were also studied in this assay. It can be concluded that zinc can be toxic to crabs only at high concentrations. Considering that levels up to 1 mg Zn L^− 1 were recently reported in Mar Chiquita coastal lagoon waters, the potential occurrence of mean chronic effects on the crab population within the coastal lagoon is discussed.     

Evaluation of the acute, chronic and teratogenic effects of a mixture of eleven pharmaceuticals on the cnidarian, Hydra attenuata

Pharmaceuticals have recently emerged as novel pollutants of potential concern in the aquatic environment where they are commonly introduced as complex mixtures via municipal effluent. In the present experiment, the freshwater cnidarian Hydra attenuata was exposed to a mixture of 11 pharmaceuticals (ibuprofen, naproxen, gemfibrozil, bezafibrate, carbamazepine, sulfapyridine, oxytetracycline, novobiocin, trimethoprim, sulfamethoxazole and caffeine) up to 10 000 times (×) the concentration found in municipal effluent. Hydra regeneration and teratogenicity was measured, having an IC₅₀ of 781× and was found to be non teratogenic with an A/D value of ∼ 1. Toxicity was investigated using both lethal (based on morphology) and sub-lethal (based on morphology, feeding behaviour, hydranth number and attachment) endpoints. The pharmaceutical mixture incurred a significant decrease in morphology at 0.1, 10 and 100× but a significant increase at 1000×. All parameters were significantly reduced at 10 000×. An EC₅₀ of 425× and 65× based on morphology and feeding respectively and a toxicity threshold (TT) of 3.2× were calculated. When compared to the toxicity of each pharmaceutical exposed individually as previously reported [Quinn B, Gagné F, Blaise C. An investigation into the acute and chronic toxicity of eleven pharmaceuticals found in wastewater effluent on the cnidarian, H. attenuata. Sci Total Environ 2008a; 389: 306-314], the compounds in the mixture were present at concentrations 2 to 3 orders of magnitude lower for the equivalent toxicity (EC₅₀ and TT). These results indicate that pharmaceuticals act additively in a mixture, having sub-lethal effects at environmentally relevant (µg/L-ng/L) concentrations and that their combined concentrations could potentially prove significantly ecotoxic to Hydra and possibly to other aquatic taxa.     

Influence of sex, maturity and reproduction on PCB and p,p′DDE concentrations and repartitions in the European hake (Merluccius merluccius, L.) from the Gulf of Lions (N.W. Mediterranean)

The main objective of this work was to establish the influence of sex, maturity and reproduction on the contamination of the demersal fish Merluccius merluccius by organochlorine compounds. Polychlorinated biphenyls (PCBs) and p,p′DDE were quantified in muscle, liver and gonads of female and male hakes collected in the Gulf of Lions in 2004 and 2005. Observed levels appeared higher than the population of the Bay of Biscay and lower than the population of the Thyrrenian Sea. Contaminant fingerprints were roughly constant whatever the studied organ and the hake biological condition. Concentrations varied significantly according to the sex and maturity of hakes. Mature specimens were more contaminated than immature, and males presented higher levels than females. This sex effect can be linked to a lower growth rate of males, and a contaminant elimination during female spawning. Gonadal contamination depends on the importance of lipid content and increases with the maturation degree. Although the main organ of energy and PCB storage is the liver, muscle appears as the main contributor to the gonad contamination.     

Effects on growth, photosynthesis and pigments of the freshwater moss Fontinalis antipyretica Hedw. after exposure to wood ash solution

The application of wood ash from biofuel sources to the forest has been suggested as a source of nutrients for trees and for restoration of acidified soils and surface waters. Studies on the effects of wood ash on aquatic organisms and ecosystems are, however, few. This study investigated the effects of wood ash (0.1-10 g l(-1)) on the freshwater moss Fontinalis antipyretica Hedw., which has previously been shown to be a sensitive test organism for assessing environmental pollution. After nine weeks of treatment with wood ash, a significant effect of enhanced stem growth was observed at higher concentrations (1-10 g l(-1)). The concentration of wood ash was also correlated with the growth of secondary branches. Photosynthesis (oxygen evolution after 4 h of exposure to wood ash) was significantly lower in the alkaline treatments (no pH adjustment) compared to the treatments with neutral wood ash solutions (pH adjusted to 7.5). Furthermore, photosynthesis in the alkaline wood ash treatments was significantly lower compared to the control. The ratio between the optical density value before and after acidification (OD(665/665a)) was higher for all wood ash concentrations compared to the control. The OD(665/665a) values ranged from 1.52 to 1.61 and there was a difference, however not significant, between the alkaline and the neutral treatment at 10 g l(-1) wood ash. This study clearly demonstrated that wood ash may be beneficial for F. antipyretica at moderate concentrations (0.5-5 g l(-1)), particularly when a sudden increase in pH is avoided.     

The comparison of two heavy fuel oils in composition and weathering pattern, based on IR, GC-FID and GC-MS analyses: Application to the Prestige wreackage

This paper compares the weathering patterns of two similar fuel oils: a fuel oil spilled after a ship accident (Prestige-Nassau, off the Galician coast -NW Spain-) and a fuel designed to cope with the numerous quests for samples to carry out scientific studies (IFO). Comparative studies were made to evaluate the capability of common fingerprinting analytical techniques to differentiate the fuels, as well as their capabilities to monitor their weathering. The two products were spilled under controlled conditions during ca. four months to assess how they evolved on time. Mid-IR spectrometry and gas chromatography (flame ionization and mass spectrometry detectors) were used. IR indexes related to total aromaticity, type of substituents (branched or linear chains) and degree of aromatic substitution reflected well the differences between the fuels during weathering. Regarding the chromatographic measurements, the n-alkanes became highly reduced for both fuel oils and it was found that the PAHs of the synthetic fuel (IFO) were more resistant to weathering. Regarding biomarkers, the different profiles of the steranes, diasteranes and triaromatic steroids allowed for a simple differentiation amongst the two products. The %D2/P2 ratio differentiated both products whereas the %N3/P2 one ordered the samples according to the extent of their weathering.