Lieven Bervoets

METAL CONCENTRATIONS IN WATER, SEDIMENT AND GUDGEON (GOBIO GOBIO) FROM A POLLUTION GRADIENT: RELATIONSHIP WITH FISH CONDITION FACTOR

This study assesses the applicability of a sentinel fish species as a biomonitor of metal pollution. Gudgeon (Gobio gobio) were collected from 14 sites in metal polluted lowland rivers in Flanders, including a clear Cd and Zn pollution gradient. Fish tissues were analysed for Cd, Cr, Cu, Ni, Pb and Zn. Metal levels in organs were related to levels in water and sediment. At some sites Cd and Zn levels were up to 50 times higher compared to reference values and literature. Significant relationships between Cd and Zn in fish tissue and environmental levels were found, especially in the pollution gradient where up to 70% of the observed variation could be described. Condition factor differed significantly among the sampling sites but could not be directly related to the environmental metal levels. Nevertheless, in the pollution gradient, threshold tissue concentrations could be defined above which the condition factor was always low.

Variation of heavy metals within and among feathers of birds of prey: effects of molt and external contamination

In this study we examined the effect of external contamination on the heavy metal (Ag, Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn) concentration in feathers. We compared the heavy metal content among the 10 primary wing feathers of sparrowhawks (Accipiter nisus), little owls (Athene nocta) and barn owls (Tyto alba) and the variation within the outermost tail feather of sparrowhawks and tawny owls (Strix aluco). The concentration of Hg was significantly higher in feathers molted first, suggesting that levels in feathers reflect levels in the blood during formation. For some other elements (Al, Co, Ni, Pb, Zn) on the other hand, there are strong indications that external contamination may have an important impact on the levels detected in the feathers. This should be taken into account in future monitoring studies.

Brominated flame retardants and perfluorinated compounds in indoor dust from homes and offices in Flanders, Belgium.

The increasing time spent indoors combined with the abundant usage of diverse indoor chemicals led to concerns involving the impact of these compounds on human health. The current study focused on two groups of important indoor contaminants i.e. Brominated flame retardants (BFRs) and Perfluorinated compounds (PFCs). Concentrations of both compound classes have been measured in Flemish indoor dust samples from homes and offices. ΣPolybrominated diphenyl ethers (PBDEs) (BDE 47, 99, 100, 154, 153, 197, 196 and 203) and BDE 209 in homes ranged between 4-1214 ng g(-1)dw (median 35) and <5-5295 ng g(-1)dw (median 313), respectively. Hexabromocyclododecane (ΣHBCD) levels ranged from 5 to 4,2692 ng g(-1)dw (median 130), with α-HBCD being the major isomer (mean 59%). In addition, tetrabromobisphenol A (TBBPA) ranged between <3 and 419 ng g(-1)dw (median 12). For all BFRs, median levels in office dust were up to an order of magnitude higher than in home dust. ΣPFCs (sum of perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonic acid (PFOS), perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA)) concentrations in homes ranged from 0.2 to 336 ng g(-1) (median 3.0 ng g(-1)). Levels in office dust were higher (p<0.01) than in house dust with ΣPFCs ranging between 2.2 and 647 ng g(-1) (median 10 ng g(-1)) and median (PFOA) and perfluorooctane sulfonate values of 2.9 and 2.2 ng g(-1), respectively. The congener pattern was dominated by PFOA, followed by PFOS. Calculated human exposure was below the reference dose values set by the US-EPA for BDE 209, HBCD and below the provisional tolerable daily intakes proposed by European Food Safety Authority for PFOS and PFOA.

Perfluorinated Substances in Human Food and Other Sources of Human Exposure

The widespread distribution and degradation of PFCs in the environment results in a very complex exposure pattern, which makes it difficult to define the relative contribution to human exposure from different exposure pathways. The present review is designed to provide an overview of the existing data on levels of PFCs measured in the human diet and in drinking water. Data on levels of PFCs in the human diet are rather scarce, but the level in the fish appear to be well documented. Among PFCs, PFOS and PFOA are the best studied compounds in fish from both experimental and monitoring studies. Recently, the number of publications that address other PFCs has increased, but the total number available is still limited. In general, we discovered that care should be exercised when using the reviewed data, because, in the majority of publications, quality control and/or details on analysis are, at least partly, lacking. It has been well documented that PFOA and PFOS have the potential to accumulate in fish and concentrations up to 7 and 170 ng/g wwt, respectively in edible fish species have been found. PFOS is the most crucial and prominent compound identified, followed by the PFOA. Also, in aquatic invertebrate such as shrimps, mussels, clams, and oysters, high PFOS levels have been reported (up to 387 ng/g wwt). However in most publications PFC level reported in molluscs were less than 1 ng/g wwt. Positive correlations were found between PFC body burden and self reported fish consumption. In recognition of the potential for human exposure to PFCs via fish consumption, the Minnesota Department of Health has recently issued fish consumption advisories for contaminated sections of the Mississippi River. It is interesting to note that 79% of the reviewed publications on PFCs in the whole fish homogenates exceed the that threshold. Moreover, five of the PFC concentration reported in muscles tissue exceeded the advisory level of 38 ng/g wwt. Even though several authors concluded that consumption of contaminated food and drinking water constitutes the major exposure pathway for humans, only a few reports on PFCs in composite food exist. Food can be contaminated in an indirect way, because PFCs are widely used in food-packaging coatings and cooking materials. On the other hand, PFCs can also enter food organisms via environmental routes such as inhalation or adsorption from air. In a few studies, composite samples, duplicate diet samples, or other food items were analyzed for several PFCs, PFOS and PFOA, PFHpA, PFHxA, and PFHxS were meAsured and displayed concentrations ranging from-detected up to 15 ng/g wwt. In one study, a very high PFOA concentration of 118 ng/g were reported, but overall, PFC levels are below 10 ng/g wwt. It is important to note that, among all studies reviewed, PFCs were found in a maximum of 50% of the analyzed samples and generally only in 10% or less of samples analyzed. In contrast to what is observed in fish and other food items PFOA levels in drinking water (ND - 50 ng/L) and other PFCs (1-3 ng/L). In one study, extremely high values (519 ng/L) were measured in drinking water of a contaminated area in the Ruhr region. In Spain, bottled water was analyzed and four PFCs (PFOA, PFNA,PFDA and PFHpA) were found at low levels (<1 ng/L). Because of higher levels found in drinking water at several locations, some provisional drinking water guideline values for PFOS and PFOA have already been established, e.g., in the UK, Bavaria, and Minnesota. Since PFCs are present both in food and drinking water, Tolerable Daily Intake values for PFOS and PFOA have also been proposed by several institutes in Europe and in the USA. The ingestion of dust through hand-to-mouth transfer from indoor house dust can also be a potential source of PFC exposure, especially for toddlers and children. In publications on PFCs in indoor dust, the mean PFOS and PFOA levels varied between 39 and 1,200 ng/g and between 11 and 220 ng/g, respectively. Overall, it is clear that there is still lack of PFC exposure data for food and beverages, which renders the assessment of the contribution of the diet to total human PFC exposure uncertain. It is, therefore, appropriate that several scientific projects have recently been launched that addresses the assessment of human exposure to PFCs and related compounds from dietary sources.

Cocaine and metabolites in waste and surface water across Belgium

Cocaine abuse, a growing social problem, is currently estimated from population surveys, consumer interviews and crime statistics. A new approach based on the analysis of cocaine (COC) and metabolites, benzoylecgonine (BE) and ecgonine methyl ester (EME), in water samples was applied to 28 rivers and 37 waste water treatment plants in Belgium using solid-phase extraction and liquid chromatography coupled to tandem mass spectrometry. While EME was undetectable, COC and BE were detectable with concentrations ranging from <1 to 753 ng/L and <1 to 2258 ng/L, respectively. BE concentrations were employed to calculate the local amount of abused cocaine. The highest values (up to 1.8 g/day cocaine per 1000 inhabitants) were found in large cities and during weekends. The estimation of cocaine abuse through water analysis can be executed on regular basis without cooperation of patients. It also gives clear geographical information, while prevention campaigns can easily be implemented and evaluated.

Sewage epidemiology : a real-time approach to estimate the consumption of illicit drugs in Brussels, Belgium

The sewage epidemiology approach was applied to a one-year sampling campaign in the largest wastewater treatment plant (WWTP) in Belgium. The consumption of cocaine (COC), amphetamine (AMP), methylenedioxymethamphetamine (MDMA), methamphetamine (METH), methadone (MTD) and heroin (HER) was evaluated based on measured concentrations of the parent compound and/or metabolites in daily 24-hour composite influent wastewater samples. The inevitable back-calculations used in the sewage epidemiology approach were adapted to newly available information regarding the stability of the compounds in wastewater and the excretion pattern of illicit drugs. For COC, three different back-calculation approaches were evaluated. In addition, for the first time, efforts were made to calculate the number of inhabitants living in the catchment area of the WWTP in a real-time and dynamic way, based on concentrations of nitrogen, phosphorus and oxygen in the wastewater samples. Clear variations in the amount of inhabitants in the catchment area of the WWTP were observed. For COC, AMP and MDMA a significant higher weekend use was observed while for HER and MTD no significant daily variations could be found. METH consumption was negligible. Generally, the sewage epidemiology calculations were in agreement with official statistics. This manuscript shows that sewage epidemiology provides consistent and logical results and that it is a promising tool that can be used in addition to classical studies to estimate illicit drug use in populations. Therefore, efforts should be made to further optimize this approach in the future.

Can cocaine use be evaluated through analysis of wastewater? A nation-wide approach conducted in Belgium.

AIMS Cocaine is the second most-used illicit drug world-wide and its consumption is increasing significantly, especially in western Europe. Until now, the annual prevalence has been estimated indirectly by means of interviews. A recently introduced and direct nation-wide approach based on measurements of the major urinary excreted metabolite of cocaine, benzoylecgonine, in wastewater is proposed. DESIGN Wastewater samples from 41 wastewater treatment plants (WWTPs) in Belgium, covering approximately 3,700,000 residents, were collected. Each WWTP was sampled on Wednesdays and Sundays during two sampling campaigns in 2007-08. Samples were analysed for cocaine (COC) and its metabolites, benzoylecgonine (BE) and ecgonine methylester (EME) by a validated procedure based on liquid chromatography coupled with tandem mass spectrometry. Concentrations of BE were used to calculate cocaine consumption (g/day per 1000 inhabitants) for each WWTP region and for both sampling campaigns (g/year per 1000 inhabitants). FINDINGS Weekend days showed significantly higher cocaine consumption compared with weekdays. The highest cocaine consumption was observed for WWTPs receiving wastewater from large cities, such as Antwerp, Brussels and Charleroi. Results were extrapolated for the total Belgian population and an estimation of a yearly prevalence of cocaine use was made based on various assumptions. An amount of 1.88 tonnes (t) per year [standard error (SE) 0.05 t] cocaine is consumed in Belgium, corresponding to a yearly prevalence of 0.80% (SE 0.02%) for the Belgian population aged 15-64 years. This result is in agreement with an earlier reported estimate of the Belgian prevalence of cocaine use conducted through socio-epidemiological studies (0.9% for people aged 15-64 years). CONCLUSIONS Wastewater analysis is a promising tool to evaluate cocaine consumption at both local and national scale. This rapid and direct estimation of the prevalence of cocaine use in Belgium corresponds with socio-epidemiological data. However, the strategy needs to be refined further to allow a more exact calculation of cocaine consumption from concentrations of BE in wastewater.

Brominated flame retardants and perfluorinated chemicals, two groups of persistent contaminants in Belgian human blood and milk.

We assessed the exposure of the Flemish population to brominated flame retardants (BFRs) and perfluorinated compounds (PFCs) by analysis of pooled cord blood, adolescent and adult serum, and human milk. Levels of polybrominated diphenyl ethers (PBDEs) in blood (range 1.6-6.5 ng/g lipid weight, lw) and milk (range 2.0-6.4 ng/g lw) agreed with European data. Hexabromocyclododecane ranged between <2.1-5.7 ng/g lw in milk. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) dominated in blood and ranged between 1 and 171 ng/mL and <0.9-9.5 ng/mL, respectively. Total PFC levels in milk ranged between <0.5-29 ng/mL. A significant increase in PBDE concentrations was detected from newborns (median 2.1) to the adolescents and adults (medians 3.8 and 4.6 ng/g lw, respectively). An identical trend was observed for PFOS, but not for PFOA. We estimated that newborn exposure to BFRs and PFCs occurs predominantly post-natally, whereas placental transfer has a minor impact on the body burden.

The impact of increased oxygen conditions on metal-contaminated sediments part I: effects on redox status, sediment geochemistry and metal bioavailability.

In order to evaluate the effect of improved oxygen concentrations in overlying surface water on the redox status, sediment geochemistry and metal bioavailability in metal-polluted sediments a 54 days lab experiment with two different experimental treatments was conducted (90% and 40% O(2)). Changes in redox potential (Eh) in the sediment were monitored over time. At 6 different time points (after 0, 2, 5, 12, 32 and 54 days) and at 4 sediment depths (0-1, 1-4, 4-8 and 8-15 cm), acid volatile sulfides (AVS), simultaneously extracted metals (SEM) and total organic carbon (TOC) were measured and metal release to overlying surface water was determined. Labile metal species in both water and sediment were measured using Diffusive Gradients in Thin films (DGT). Our results showed that elevated oxygen levels in overlying surface water led to an Eh increase in the sediment of the 90% O(2) treatment from 0 to ± 200 mV while AVS concentrations in the upper sediment layer decreased by 70%. Following AVS oxidation metal availability in the pore water was highly elevated after 54 days. However, Cu remained strongly bound to the sediment during the whole experiment. Only a limited metal release to the overlying surface water was noticed, which was due to the fact that SEM(tot) concentrations in the sediment did not yet exceeded AVS levels ([SEM(tot) - AVS]/f(OC) = 0) after 54 days. Additionally, adsorption on Fe and Mn hydroxides and particulate organic carbon also slowed down any potential metal release. Our results indicated that increasing oxygen concentrations due to general water quality improvements can enhance the mobility of trace metals which may result in the leaching of sediment-bound metals to overlying surface water, even in undisturbed watercourses.

Responses of aquatic organisms to metal pollution in a lowland river in Flanders : A comparison of diatoms and macroinvertebrates

The role of macroinvertebrates and diatoms as indicator for metal pollution was investigated by assessing both biota along a metal gradient in the Belgian river the Dommel. Macroinvertebrates and diatoms were sampled in summer and winter and physical-chemical characteristics of the water were measured at four different sample periods and related to sediment characteristics. Although metal concentrations, except cadmium, in the water nowhere exceeded water quality standards, high metal concentrations were measured in the sediment, indicating historical contamination of the Dommel. At the sites that were situated downstream of the pollution source, high levels of conductivity and chloride were measured in the water. Redundancy Analysis (RDA) indicated pH, phosphate and zinc as the significant environmental variables explaining each respectively 7.7%, 11.6% and 22.6% of the macroinvertebrate community composition. Two clusters could be separated, with Gammarus pulex, Leptocerus interruptus, Baetis rhodani and Cloeon dipterum associated with low zinc concentrations and Tubificidae, Asellus aquaticus, Erpobdella sp. and Chironomus thummi-plumosus associated with higher zinc concentrations. Ammonium (10.6%), conductivity (16.5%), chloride (11.4%) and zinc (5.9%) turned out to be significant variables explaining the diatom community structure. Based on physical-chemical differences and species composition, three different groups could be separated. With this Tabellaria flocculosa and Fragilaria capucina var. rumpens were associated with low metal concentrations, Gomphonema parvulum and Nitzschia palea with elevated concentrations and Eolimna minima and Sellaphora seminulum with high zinc concentrations. In conclusion, the diatom community best reflected the metal gradient. With regard to water quality indices, those based on macroinvertebrates best followed the metal pollution gradient and were most strongly correlated with physical-chemical variables of water and sediment. This study indicated that to assess the effect of metal pollution in lowland rivers, the combined use of macroinvertebrates and diatoms is more appropriate than the use of both biota separately.