Concentrations and specific loads of brominated flame retardants in sewage sludge.

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. The present study focuses on two classes of brominated flame retardants: polybrominated diphenyl ethers (BDE28, BDE47, BDE49, BDE66, BDE85, BDE99, BDE100, BDE119, BDE138, BDE153, BDE154, BDE183, BDE209) and hexabromocyclododecane (HBCD) detected in sewage sludge collected from a monitoring network in Switzerland. Mean concentrations (n=16 wastewater treatment plants) were 310, 149, 95 and 17microg per kg dry matter for decaBDE, HBCD, penta- and octaBDE, respectively. These numbers correspond well with other studies from European countries. DecaBDE, HBCD, penta- and octaBDE showed average specific loads (load per connected inhabitant per year) in sludge of 6.1, 3.3, 2.0 and 0.3mgcap(-1)yr(-1), respectively. This is in line with consumption and storage of the compounds in the environment and the anthroposphere. Discrepancies observed for octaBDE and HBCD can be explained by the release from materials where these compounds are incorporated in and/or their degradation during anaerobic sludge treatment. Loads from different types of monitoring sites showed that brominated flame retardants ending up in sewage sludge originate mainly from surface runoff, industrial and domestic wastewater.

Organic pollutants in compost and digestate. Part 1. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and molecular markers.

In Europe, 9.3 x 10(6) t(dry weight (dw)) of compost and digestate are produced per year. Most of this is applied to agricultural land, which can lead to considerable inputs of organic pollutants, such as polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) to soil. This paper presents an inventory of the pollutant situation in source-separated composts, digestates and presswater in Switzerland by a detailed analysis of over 70 samples. PCB concentrations ( summation PCB 28, 52, 101, 118, 138, 153, 180) were significantly higher in urban (median: 30 microg kg(-1)dw, n = 52) than in rural samples (median: 14 microg kg(-1)dw, n = 16). Together with low concentrations in general, this points to aerial deposition on compost input material as the major contamination pathway. Enantiomeric fractions of atropisometric PCB were close to racemic. Median PAH concentration was 3010 microg kg(-1)dw( summation 15PAH, n = 69), and one quarter of the samples exhibited concentrations above the relevant Swiss guide value for compost (4000 microg kg(-1)dw). The levels were influenced by the treatment process (digestate > compost), the season of input material collection (spring-summer > winter > autumn), the particle size (coarse-grained > fine-grained), and maturity (mature > less mature). The main source of PAH in compost was pyrogenic, probably influenced mainly by liquid fossil fuel combustion and some asphalt abrasion, as suggested by multiple linear regression. This study, together with a companion paper reporting on other organic contaminates including emerging compound classes, provides a starting point for a better risk-benefit estimation of the application of compost and digestate to agricultural soil in Switzerland.

Organic pollutants in compost and digestate. Part 2. Polychlorinated dibenzo-p-dioxins, and -furans, dioxin-like polychlorinated biphenyls, brominated flame retardants, perfluorinated alkyl substances, pesticides, and other compounds.

Compost and digestate are important recycling fertilizers and have beneficial effects on soil parameters. However, they can contain significant amounts of organic pollutants. Here, the first comprehensive data set on dibenzo-p-dioxins and -furans (PCDD/F), dioxin-like polychlorinated biphenyls (DL-PCB), brominated flame retardants, perfluorinated alkyl substances (PFAS), pesticides, phthalates, nonylphenol and chlorinated paraffins (CP) in source-separated compost and digestate from Switzerland is presented (n = 3-18). The median summation 17PCDD/F and summation 12DL-PCB concentrations were at 3.2 ng I-TEQ kg(-1)dry weight (dw) and 3.0 ng WHO-TEQ kg(-1)dw, respectively. Brominated diphenyl ether 209 (BDE 209) accounted for 72% of the total polyBDE content (10 microg kg(-1)dw). Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) levels were at 100 and 0.51 microg kg(-1)dw, respectively. PFAS were identified for the first time in compost and digestate (median concentration 6.3 microg kg(-1)dw, summation 21compounds). Out of 269 pesticides analysed, 30 fungicides, 14 herbicides, eight insecticides and one acaricide were detected. Di-(2-ethylhexyl)phthalate (DEHP) median concentration accounted for 280 microg kg(-1)dw and nonylphenol was below the detection limit of 1 mg kg(-1)dw. The sum of short and medium chain CP was between 90 and 390 microg kg(-1)dw. The concentrations observed were at or above the levels found in background soils, which are the main recipient of compost and digestate. Where actually applied, compost can contribute considerably to the total input of organic pollutants to the soil. However, on a total Swiss agricultural area base, inputs seem to be limited.

Multigeneration effects of insect growth regulators on the springtail Folsomia candida.

Multigeneration tests are very useful for the assessment of long term toxicity of pollutants such as endocrine disruptor compounds. In this study, multigeneration reproduction tests adapted from the ISO standard 11267 were conducted with the Collembola Folsomia candida. Springtails were exposed to artificial soil contaminated with four insect growth regulators (methoprene, fenoxycarb, teflubenzuron, and precocene II) according to two different experimental set-ups. In the first set-up, the parental generation (F(0)) of Collembola was exposed to a pollutant for 28 days. Juveniles from the F(1) generation were transferred to uncontaminated soil for another 28-day period to generate the F(2) generation. In the second set-up, the F(0) generation was exposed to a pollutant for 10 days before being transferred to uncontaminated soil to reproduce. After 18-28 days, juveniles from the F(1) were transferred to clean soil to generate the F(2) generation. An effect on the number of hatched juveniles of the F(2) generation was observed for methoprene after exposure of the F(0) for 28 days and hatching of F(1) in contaminated soil. For methoprene and teflubenzuron, significant effects were even observed on the F(2) generation with the second experimental set-up, when only the F(0) generation was exposed for 10 days. This shows that the impact of these substances is transgenerational, which can have important consequences for the population of these or other organisms. No effect on the F(2) generation was observed with fenoxycarb and precocene II with the 10-day exposure experiment. Our results show that the developed experimental procedures are appropriate to assess the long term effects of endocrine disrupting compounds on the reproduction of the non-target species F. candida. Another important finding is that two substances with the same predicted mode of action (i.e., the two juvenile hormone analogues fenoxycarb and methoprene) do not necessarily affect the same endpoints in F. candida.

Dioxin contamination in soils of Southern Vietnam.

Dioxin is the common name for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), and is abbreviated as PCDD/Fs. In the case of Southern Vietnam, is of high concern dioxin contamination in the areas affected by past-use chemical defoliants. Our study related to the zone considered as a "hot spot"--Bien Hoa Airbase and surrounding areas (Bien Hung Lake). Although the war ended over 30 years ago, the adverse effects on this territory still continue. Soil and sediment were selected for our research as they act as a sink for PCDD/Fs. The samples were taken and analyzed in CECOTOX laboratory following certified procedures. The total amounts of PCDD/Fs (2,3,7,8 related congeners) in the samples were converted into WHO-TEQ and compared with standard values proposed by Canadian environmental quality guidelines. The obtained data shows a relatively high risk (up to 20.4 times higher than (probable effect level) PEL value for sediment and 46 times higher than standard value for soil). The research is continuing on the assessment of dioxin transport in food chain. Moreover, considering the obtained data a complete solution should be found urgently to solve the problem of dioxin contamination in the studied areas.

Fate of PCBs, PAHs and their source characteristic ratios during composting and digestion of source-separated organic waste in full-scale plants.

Composting and digestion are important waste management strategies. However, the resulting products can contain significant amounts of organic pollutants such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). In this study we followed the concentration changes of PCBs and PAHs during composting and digestion on field-scale for the first time. Concentrations of low-chlorinated PCBs increased during composting (about 30%), whereas a slight decrease was observed for the higher chlorinated congeners (about 10%). Enantiomeric fractions of atropisomeric PCBs were essentially racemic and stable over time. Levels of low-molecular-weight PAHs declined during composting (50-90% reduction), whereas high-molecular-weight compounds were stable. The PCBs and PAHs concentrations did not seem to vary during digestion. Source apportionment by applying characteristic PAH ratios and molecular markers in input material did not give any clear results. Some of these parameters changed considerably during composting. Hence, their diagnostic potential for finished compost must be questioned.

Effects of dinoseb on energy reserves in the soil arthropod Folsomia candida.

This study evaluated the usefulness of energy reserves as an early warning system in Folsomia candida when exposed to the pesticide dinoseb. After different exposure times, survival, reproduction, growth (weight and length), lipid and protein content of the organisms were determined. After six days of exposure at 15-30microg of dinoseb/g dry soil, the weight, lipid, and protein content of the exposed organisms were higher than the controls. This stimulation seems to indicate that Collembola adopt a strategy of increasing their growth in order to improve their reproduction. This hypothesis was confirmed by the number of eggs laid which was greater in exposed organisms. After 21 days, all measured parameters decreased. The results show that after having produced an effort to increase growth and reproduction, lethality increases. The selected energy reserves are not more sensitive than the classically measured parameters such as reproduction, but can be more predictive for a pollutant stress encountered by the organisms.

Concentrations and specific loads of UV filters in sewage sludge originating from a monitoring network in Switzerland.

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. The present study focuses on the analysis of widely used UV filters 3-(4-methylbenzylidene) camphor (4-MBC), octyl-methoxycinnamate (OMC), octocrylene (OC) and octyl-triazone (OT) in sewage sludge originating from a monitoring network in Switzerland. Mean concentrations in stabilised sludge from 14 wastewater treatment plants were 1780, 110, 4840 and 5510 microg/kg dry matter for 4-MBC, OMC, OC and OT, respectively. Specific loads in sewage sludge show that UV filters originate mainly from private households, but surface runoff and industries may be considered as additional sources. This indicates that besides use for sunscreens and cosmetics UV filters might occur in plastics and other materials and be released to the environment by volatilization or leaching. Differences between the modeled per capita loads of UV filters in sewage sludge and the observed specific loads in sewage sludge are probably due to erroneous figures of production volumes, degradation and sorption during wastewater treatment as well as degradation processes during transport in the sewer or sludge treatment. Thus, further research is needed to elucidate the fate of UV filters after application and release into the environment. Other compounds used as UV filters should be included in future studies.

Modeling the concentration-response function of the herbicide dinoseb on Daphnia magna (survival time, reproduction) and Pseudokirchneriella subcapitata (growth rate).

Models describing dose-response relationships are becoming increasingly popular in ecotoxicology. They allow simple and thorough evaluations of toxicity test results, including inter- and extrapolations to concentrations or exposure times other than those tested. Simple parametric regression models are of particular interest because their parameters may be attributed mechanistic meanings and they can be applied without sophisticated mathematical and computational support. We recently proposed a four-parameter logistic regression model to fit the survival data of Daphnia magna under dinoseb stress. The model parameters are the maximum survival time, the minimum time required for an individual to die, effect concentration, EC(50), and a curve shape parameter. This model has now been applied to compare the lethality and reproduction toxicity of D. magna and the growth inhibition of Pseudokirchneriella subcapitata under dinoseb stress. It can be fitted adequately to all the measured data and the parameters can be attributed biological meanings in any of the three endpoints. A comparison of the modeled concentration-response functions of all three endpoints for dinoseb toxicity shows that the range of ECs with respect to both D. magna and algae is steep (a decrease of between 0.1 and 0.6 mg/L). The survival and reproduction of D. magna exhibit similar characteristic concentration-response functions and toxicities. The statistical no-effect concentration (SNEC) is 0.14 (survival) and 0.11 (reproduction)mg/L, respectively. On the other hand, algae seem to be less sensitive to dinoseb than D. magna (SNEC: 0.48 mg/L). However, further investigations of individual algae may lead to a more suitable comparison. We speculate that the four parameters of the model function can be related to specific properties of chemicals and organisms. Characterization of these properties would allow simple and appropriate estimation of the toxic effects of these chemicals.

Persistent organic pollutants in source-separated compost and its feedstock materials--a review of field studies.

Composting and the application of compost to the soil follow the principle of recycling and sustainability. Compost can also have a positive effect on physical, chemical, and biological soil parameters. However, little is known about the origin, concentration, and transformation of persistent organic pollutants (POPs) in compost. We therefore compiled literature data on some priority POPs in compost and its main feedstock materials from more than 60 reports. Our data evaluation suggests the following findings. First, median concentrations of Sigma 16 polycyclic aromatic hydrocarbons (PAHs), Sigma 6 polychlorinated biphenyls (PCBs), and Sigma 17 polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) were higher in green waste (1803, 15.6 microg/kg dry wt., and 2.5 ng international toxicity equivalent [I-TEQ]/kg dry wt.) than in organic household waste (635, 14.6 microg/kg dry wt., and 2.2 ng I-TEQ/kg dry wt.) and kitchen waste (not available [NA], 14.9 microg/kg dry wt., 0.4 ng I-TEQ/kg dry wt.). The POP concentrations in foliage were up to 12 times higher than in other feedstock materials. Second, in contrast, compost from organic household waste and green waste contained similar amounts of Sigma 16 PAHs, Sigma 6 PCBs, and Sigma 17 PCDD/Fs (1915, 39.8 microg/kg dry wt., and 9.5 ng I-TEQ/kg dry wt., and 1715, 30.6 microg/kg dry wt., and 8.5 ng I-TEQ/kg dry wt., respectively). Third, concentrations of three-ring PAHs were reduced during the composting process, whereas five- to six-ring PAHs and Sigma 6 PCBs increased by roughly a factor of two due to mass reduction during composting. Sigma 17 PCDD/Fs had accumulated by up to a factor of 14. Fourth, urban feedstock and compost had higher POP concentrations than rural material. Fifth, the highest concentrations of POPs were usually observed in summer samples. Finally, median compost concentrations of POPs were greater by up to one order of magnitude than in arable soils, as the primary recipients of compost, but were well within the range of many urban soils. In conclusion, this work provides a basis for the further improvement of composting and for future risk assessments of compost application.

Tropical ecotoxicity testing with Ceriodaphnia cornuta.

The Sai Gon-Dong Nai river system in southern Vietnam is of great social and economic importance yet receives a large amount of industrial, domestic, and agricultural discharges. Toxicity assessment has started to become an issue in Vietnam, and it is important to employ a test system that is appropriate for typical Vietnamese conditions with a species that is representative of the invertebrates living in its aquatic ecosystems. The aim of this study was to develop and to validate an ecotoxicity test with an autochthonous organism. The microcrustacean Ceriodaphnia cornuta (Cladocera) was isolated from the Sai Gon River. A protocol was developed for the culturing of the organisms, and satisfactory results were obtained for long-term reproduction of C. cornuta. Quality control criteria were established. The toxicity of two relevant pesticides (diazinon and methyl parathion) and two metals (chromium and mercury) to C. cornuta was evaluated and compared to the standard organisms for ecotoxicological testing: Daphnia magna and Vibrio fischeri. Nonlinear regression models were applied to estimate such parameters as EC(50). The results of acute toxicity tests showed that C. cornuta was less tolerant than D. magna and V. fischeri to salinity and that C. cornuta was more sensitive than D. magna and V. fischeri to potassium dichromate, diazinon, methyl parathion, and mercury.

Urban stormwater contamination by polychlorinated biphenyls (PCBs) and its importance for urban water systems in Switzerland.

Like other persistent organic pollutants (POPs), polychlorinated biphenyls (PCBs) are still present in the environment despite their almost worldwide prohibition. A study was conducted over 1 year in Switzerland to analyze the source and load of PCBs in urban stormwater and their importance in urban water systems. The mean PCB concentrations of 89 rain events were determined in five different strictly separate drainage systems (three in Lausanne and two in Geneva). The mean concentrations of PCBs in stormwater ranged from values below the detection limit (0.11-0.24 ng/l) to 403 ng/l. A model for the wet and dry deposition of PCBs based on these results estimates that their concentration in rainwater has remained practically constant (35 ng/l) over a period of 12 years. A mass balance of Swiss levels estimates a total input load of PCBs in the urban water systems at 110-125 kg/year. The contribution of stormwater is 75-94 kg/year in combined sewer systems and 23-34 kg in separate sewer systems. This mass balance illustrates that a major part of the PCB load in the environment or in WWTP sludges originates from urban stormwater. This result was confirmed by a fingerprint of PCB congeners in stormwater, which showed a pattern identical to that found in sewage sludge in combined sewer systems.

Hsp70 instability and induction by a pesticide in Folsomia candida.

The heat shock protein Hsp70 has been shown to be a promising biomarker in aquatic and terrestrial organisms. However, its analysis in the soil insect Folsomia candida (Collembola) poses many problems as the protein is particularly unstable in this species. Western blotting has shown that the principal degradation fragment has a size of 48 kDa. We have developed a Western blot method that avoids the degradation of Hsp70 and was successful in detecting the protein in the springtail F. candida after a heat shock (12, 18 and 24 h at 32 degrees C). In the second part of the study the organisms were exposed to artificial compressed soil contaminated with the dinitrophenol dinoseb (10, 15 and 20 micrograms g-1 dry weight [DW]). Hsp70 was analysed in pooled samples (40 to 150 collembola according to age) after 1, 2, 3, 4, 5, 6, 7, 11 and 14 days. The only significant induction was observed after 5 days at 20 micrograms g-1 DW of dinoseb. The induction patterns over time were dissimilar for the different concentrations and a relatively high variability between the replicates was observed. Our results show that we must be cautious when interpreting biomarker results, especially those for Hsp70.

Effects of dinoseb on the life cycle of Daphnia magna: modeling survival time and a proposal for an alternative to the no-observed-effect concentration.

Risk assessment is in urgent need of more accurate toxic effect endpoints than those currently in use, especially for low concentrations. Often such endpoints are estimated by analysis of variance, linear interpolation, or smoothing. As these statistical methods are not always satisfactory, some authors have proposed to describe the entire dose-response curves by fully formalized parametric regression models whose parameters have toxicological meaning. These models allow a better evaluation of pollutant effects, including inter- and extrapolation to any other than the measured effect values. Following this line, a four-parameter logistic regression model (standard model) was fitted to survival data of Daphnia magna under pesticide (dinoseb) stress. The heterogeneity of the variance was taken into account with a both-sides logarithmic transformation. Besides the standard model, a hormesis and a threshold model were tested too. These two others models have been described in the literature and might better represent the dose-response function we are looking for. All three models showed a good fit to our data, and the statistics gave no hints as to which model is the most appropriate. As no evidence was seen for hormesis or for the existence of a threshold concentration, we used the simplest, namely, the standard model, for most of our calculations. Model calculations allow the quantification of the effects on individuals' longevity as well as on mean survival time of the population. We used them to define a no-effect value, the statistical-no-effect concentration (SNEC). The SNEC is based on the confidence bands of the modeled regression and represents the highest value for which an effect is statistically not different from the control. The SNEC is an alternative to classical endpoints, like the no-observed-effect concentration (NOEC) or the low-effect concentrations (e.g., EC10, EC5, EC1).

Contaminacion del Lago de Yojoa ( Honduras) por metales pesados / Lake Yojoa contamination by heavy metals (Honduras)

Located at the west center of Honduras, lake Yojoa, with an area of 89 km2 is an important natural reservoir for drinking water and irrigation. Fishing is also essential for the economy of the local population. The erosion of shores and the imput of the process water from the mine of El Mochito, located near the main river running into the lake, seem to be the reasons of a pollution by heavy metals. From december 1988 to may 1989 four metals were analysed by atomic absortion on 31 samples of sediment and 26 samples of fish. The concentrations observed in the center of the lake looks dangerous for lead (2600mg/g d.w.) and zinc (1800 mg/g d.w.) and hight for copper ( 380 mg/g d.w.) and cadmium ( 18mg/g d.w.). However, the samples of fish analysed did not present higher concentration of these metals. This result suggest that, until now, most of these heavy metals are inmobilized in the sediment.