European Environmental Quality Standards Research Articles

Occurrence and removal of micropollutants in full-scale aerobic, anaerobic and facultative wastewater treatment plants in Brazil

This study aims to evaluate micropollutant occurrence and removal in a low-middle income country (LMIC) by investigating the occurrence of 28 chemicals from different classes (triclosan, 15 polycyclic aromatic hydrocarbons (PAHs), 4 estrogens and 8 polybrominated diphenyl ether (PBDE) congeners) in three technologically diverse full-scale Brazilian wastewater treatment plants (WWTPs). These chemicals were detected at concentrations similar to those reported in other low-middle income countries (LMICs) and high-income countries (HICs) (0.1–49 μg/L) indicating their widespread use globally and the need for more studies in LMICs that are typically characterized by relatively inadequate wastewater treatment barriers. Among the three different WWTPs investigated for removal of these chemicals, the least energy intensive system, waste stabilization ponds (WSPs), was the most effective (95–99%) compared to the activated sludge (79–94%), and Up-flow sludge blanket reactor (UASB) with trickling filters system (89–95%). These results highlight the potential of WSPs for micropollutant removal-especially in warm climates. However, the effluent from all three WWTP could pose a risk to aquatic organisms when discharged into the receiving waters as the effluent concentrations of triclosan, some estrogens, PAHs and BDE 209 were above European environmental quality standards (EQS) or predicted no effect concentration (PNEC values), indicating that receiving water bodies could benefit from further treatment. In combination, these results help to further understand prevailing concentrations of micropollutants globally and fate in current wastewater treatment systems.

Application of equilibrium passive sampling to profile pore water and accessible concentrations of hydrophobic organic contaminants in Danube sediments

Total concentrations of hydrophobic organic contaminants (HOCs) in sediment present a poor quality assessment parameter for aquatic organism exposure and environmental risk because they do not reflect contaminant bioavailability. The bioavailability issue of HOCs in sediments can be addressed by application of multi-ratio equilibrium passive sampling (EPS). In this study, riverbed sediment samples were collected during the Joint Danube Survey at 9 locations along the Danube River in 2013. Samples were ex-situ equilibrated with silicone passive samplers. Desorption isotherms were constructed, yielding two endpoints: pore water (CW:0) and accessible (CAS:0) concentration of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers in sediment. CW:0 concentrations of DDT and its breakdown products exhibited elevated levels in the low Danube, with the maximum in the river delta. Other investigated HOCs did not show any clear spatial trends along the river, and only a moderate CW:0 variability. CAS:0 in sediment ranged from 10 to 90% of the total concentration in sediment. CW:0 was compared with freely dissolved concentration in the overlaying surface water, measured likewise by passive sampling. The comparison indicated potential compound release from sediment to the water phase for PAHs with less than four aromatic rings, and for remaining HOCs either equilibrium between sediment and water, or potential compound deposition in sediment. Sorption partition coefficients of HOC to organic carbon correlated well with octanol-water partition coefficients (KOW), showing stronger sorption of PAHs to sediment than that of PCBs and OCPs having equal logKOW. Comparison of CW:0 values with European environmental quality standards indicated potential exceedance for hexachlorobenzene, fluoranthene and benzo[a]pyrene at several sites. The study demonstrates the utility of passive sampling as an innovative approach for risk-oriented monitoring of HOCs in river catchments.

Natural estrogens in surface waters of a catchment with intensive livestock farming in Switzerland.

Natural estrogens such as 17α-estradiol (E2α), 17β-estradiol (E2β), estrone (E1), and estriol (E3), released to surface waters from both urban and agricultural sources, are endocrine disrupting for fish. Here, we assess the prevalence of livestock farming derived natural estrogens in tributaries and ponds in the agriculturally dominated catchment of Lake Baldegg, Switzerland. Passive samplers were deployed in the main tributary and daily time-proportional water samples were collected in five tributaries for 30 days at the beginning of the vegetation period. Furthermore, we took grab samples of 12 ponds in the catchment. Aqueous samples were liquid-liquid extracted, derivatized, and analysed with LC-MS/MS and stream water samples additionally with ERα-CALUX, a bioassay for assessing total estrogenic activity. Natural estrogens were regularly detected, with mean concentrations ranging from below the limit of detection to 0.55 ng L-1 for E2β and E1, respectively, and passive sampling and bioassay results largely confirmed these findings. Monte Carlo simulated mean natural estrogen concentrations underestimated measured ones by a factor of three to 11. An agricultural area's hydrological contribution and connectivity to surface waters seemed to be more important for the development of estrogen concentrations in streams than livestock densities in a catchment or the actual loads of slurry applied. Pond water occasionally contained natural estrogens in concentrations up to 8.6 ng L-1 for E2α. The environmental quality standards of the European Union (0.4 ng L-1 for E2β and 3.6 ng L-1 for E1) were never exceeded for longer than a day in tributaries, but E1 reached critical concentrations for aquatic organisms in ponds.

Removal efficiency and mass balance of polycyclic aromatic hydrocarbons, phthalates, ethoxylated alkylphenols and alkylphenols in a mixed textile-domestic wastewater treatment plant

In this work the occurrence and fate of polycyclic aromatic hydrocarbons (PAHs), phthalic acid esters (PAEs), mono and diethoxylate alkylphenols (AP1–2EOs) and alkylphenols (APs) have been investigated during a two-weeks period in a facility treating mixed textile-domestic wastewater (Prato, Italy). The wastewater treatment plant (WWTP) consists of primary sedimentation, activated sludge biological oxidation, secondary sedimentation, clariflocculation and ozonation. The sludge is treated within the facility by thickening, dewatering and final incineration, thus providing the almost quantitative removal of the adsorbed micropollutants. Naphthalene (50%), di(2-ethylhexyl) phthalate (74%) and branched 4-nonylphenols (59%) were the individual main representative compounds of each class in the influent wastewater, which showed concentration ranges of 5.6–66, 85–290 and 21–133μg/L for PAHs, PAEs and APs+AP1–2EOs, respectively. The WWTP efficiently removed PAHs, PAEs and APs+AP1–2EOs, providing effluent concentrations of 0.075–0.16ng/L 0.38–9.9μg/L and 0.53–1.4μg/L. All targeted priority and priority-hazardous micropollutants showed effluent concentrations in line with the European environmental quality standards (EQS), even though for di(2-ethylhexyl) phthalate and benzo(a)pyrene after correction for the dilution factor of the recipient. The WWTP performance was evaluated by mass balance, verifying its accuracy by monitoring Pb and Cd as conservative species. The biological treatment sections provided mass losses of 85.5%, 74.5% and 56.8% for APs+AP1–2EOs, PAEs and PAHs, highlighting efficient biotransformation performances of the activated sludge process. However, for the more volatile PAHs (e.g. naphthalene), a significant contribution of stripping cannot be excluded. A remarkable mass loss was also determined in the ozonation stage for PAEs (72.9%) and especially PAHs (97.0%), whereas a lower efficiency was observed for APs+AP1–2EOs (41.3%). The whole plant allowed for obtaining an almost quantitative removal (96.7–98.4%) for all targeted compounds.

Baseline tissue levels of trace metals and metalloids to approach ecological threshold concentrations in aquatic macroinvertebrates

Within the framework of the European Environmental Quality Standards Directive, the biota was recognized as a suitable matrix for monitoring water quality. In the Nalón River basin (North Spain), a catchment subject to historical mining activities, ten macroinvertebrate taxa (4 mayflies, 1 perlid stonefly, 2 caddisflies, 2 oligochaete worms, and 1 blackfly) were collected from unpolluted reference sites in the study area, and the sites were assessed as having High or Good ecological status based on their macroinvertebrate communities to establish a metal bioaccumulation reference condition. For each taxon, tissue concentrations of seven metals (Cd, Cr, Cu, Hg, Ni, Hg, and Zn) and two metalloids (As and Se) were measured and interpreted as natural baseline tissue concentrations that reflected the natural variability of the region. The taxa selected as biomonitors represented 5 different feeding styles in the benthic community: deposit-feeders, scrapers, filterers, generalists and predators, and bioaccumulation was analyzed both by taxon and feeding style as well as general habits (endo- vs epi-benthic) and river type. For each taxon, ecological threshold tissue concentrations (ETTC) were calculated as the 90th percentile (P90) of the baseline data distribution. In most instances, the deposit-feeders (aquatic lumbricid and microdrile oligochaetes) showed the highest ETTCs, except for Cu and Zn, which were mainly bioaccumulated by generalist Ephemerellidae, followed by scraper Heptageniidae in the case of Cu. The P90 values were derived from organisms in unaltered reference conditions as estimates of the no-observed-effect concentrations (NOEC), and should provide an approach to ETTCs for the field macroinvertebrate taxa of the region below which the alteration of the benthic community is unlikely. For each metal and metalloid, the P90s for the 10 taxa were entered in a species-sensitivity-distribution model, and the median hazard concentration (HC50) for the macroinvertebrate community was calculated. The ecological threshold concentrations in the biota calculated in this study are proposed for use as a screening tool in the environmental risk assessment of the Nalón River basin and the Cantabrian region, allowing metal exceedance in the selected biomonitors to further research using other lines of evidence under the European Water Framework directive.

How do measured PBDE and HCBD levels in river fish compare to the European Environmental Quality Standards?

This study evaluates the current situation regarding PBDE and HBCD levels in different river fish species. We collected published data in the last five years in different countries around the world. These levels of pollution were compared with Environmental Quality Standards (EQS) for biota established by the European Directive in the field of water policy. Although HBCD situation is not critical, with only some values exceeding the limit about 5 times, the PBDE levels clearly exceeded the established EQS, with 25% of fish samples exceeding up to ten thousand times. Although it is expected that levels of pollution by PBDEs will decrease over the next years due to the ban in their use, it is not expected that this decrease will reach the EQS values by the end of 2021, as demanded by the European Directive. Hence, it is necessary to implement new strategies in order to minimize the impact of PBDEs on the environment.

Chemical effects of a near-to-nature detention pond on a small urban headwater

The near-to-nature approach has been established as best practice for stormwater management. However, pollutant mobility within such systems and its impact on small receiving waters are partly unexplained. The study takes place in an urbanised headwater catchment in south-western Germany with an area of 0.4 km 2 . Runoff from roofs, roads, parking lots and gardens is collected in wells or trenches and stored in private and public dry detention basins. Accordingly, this study investigates pollutant input to a detention pond, removal efficiency and the associated effects on the receiving water. Grab samples with high temporal resolution of the receiving water (16 flood events with 315 samples and 41 baseflow samples), the three inflows of the detention basin and its outflow (four flood events with 64 samples) were taken. The outflow of the dry pond is recovered in the hydro- and chemographs of the receiving water. Runoff from roads with increased traffic volume caused the highest PAH inputs and runoff from the residential area showed the highest zinc concentrations, which partly infringe European Environmental Quality Standards. Yearly pollutant inputs (DOC, TSS, PAH, nutrients, metals) from the settlement into the tributary are reduced in the detention pond by up to 80%.

Trace metal concentration and fish size: Variation among fish species in a Mediterranean river

Concentration of trace metals (Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb and As) in the muscle of six fish species was analyzed to determine the variation with fish size and fish species in an Iberian river with moderate metal pollution. Al, Fe and Zn were the most abundant metals across sites. Fish size and sampling site explained more variation than fish species, and a high intraspecific variability (among individuals) in metal loads was also observed. Considering the most spread species, concentrations were highest in bleak (Alburnus alburnus) and lowest in gudgeon (Gobio occitaniae) for all the elements. Metal loads were comparable with literature data from contaminated sites, often exceeding recommended European Environmental Quality Standards. The relationships between metal concentration and fish size varied markedly among sites, elements, and fish species. The slopes of these relationships were often significantly heterogeneous, a fact barely acknowledged in the literature, and were often negative, probably due to size-specific metabolic rates related to fish growth.

Risk assessment of pesticides detected in surface water of the Alqueva reservoir (Guadiana basin, southern of Portugal)

The purpose of this study was to evaluate the potential impact of the pesticides detected in the Alqueva reservoir (Guadiana Basin, South Iberian Peninsula) on the aquatic organisms belonging to this ecosystem. For this purpose, the occurrence and risk assessment of 25 pesticides and of a number of their degradation products were determined in the Alqueva surface waters. The areas (sampling stations) most polluted by pesticides were Sra. Ajuda, Lucefecit and Álamos in the northern and in the middle portions of the reservoir, respectively. The aquatic risk assessment revealed that from the various compounds analysed terbuthylazine, chlorfenvinphos and diazinon presented non-acceptable risk when maximum concentrations were used as the measured environmental concentrations (MEC). The locations that had more samples with risk quotients higher than 1 (high risk) were Sra. Ajuda followed by Lucefécit. The use of risk assessment allowed us to conclude that, despite that the pesticides' concentrations in the water column fulfil the European environmental quality standards, a number of the compounds show a high ecotoxicological risk for the aquatic organisms in the Alqueva ecosystem. The results thereby demonstrate that to have an efficient risk management process, the regulatory authorities of each country must consider an integrative chemical and ecotoxicological approach.

Effects of Water Contamination on Site Selection by Amphibians: Experiences from an Arena Approach With European Frogs and Newts

Pesticide residues in breeding ponds can cause avoidance by at least some amphibian species. So far, outdoor experiments have been performed only with artificial pools in areas where the focus species usually occur and new colonization has been observed. Results of this kind of study are potentially influenced by natural disturbances and therefore are of limited comparability. We used an easily manufactured and standardizable arena approach, in which animals in reproductive condition for some hours had a choice among pools with different concentrations of a contaminant. Because there has been much debate on the potential environmental impacts of glyphosate-based herbicides, we investigated the impact of glyphosate isopropylamine salt (GLY-IS), Roundup LB PLUS (RU-LB-PLUS), and glyphosate's main metabolite aminomethylphosphonic acid (AMPA) on individual residence time in water. The following European amphibian species were tested: Common frog (Rana temporaria), Palmate newt (Lissotriton helveticus), and Alpine newt (Ichthyosaura alpestris). The residence time in water was not significantly affected by concentrations below or slightly above the European Environmental Quality Standards for AMPA or the German "worst-case" expected environmental concentrations for GLY-IS and RU-LB-PLUS. Occasionally, microclimatic cofactors (nightly minimum ground temperature, water temperature) apparently influenced the residence time. The major drawback of such quick behavior studies is that results can only be transferred to perception and avoidance of contaminated water but not easily to site selection by amphibians. For example, testing oviposition site selection requires more natural water bodies and more time. Hence, to develop a standard procedure in risk assessment, an intermediate design between an arena approach, as presented here, and previously performed field studies should be tested.

Spatiotemporal Variation and Risk Assessment of Pesticides in Water of the Lower Catchment Basin of Acheloos River, Western Greece

A three-year monitoring survey (March 2005–February 2008) was conducted to investigate, on monthly basis, the presence of thirty pesticides belonging to various categories and metabolites, in Acheloos River (Western Greece), one of the most important water resources in Greece. Six sampling stations along the river were established. Water analyses were performed using solid-phase extraction combined with gas chromatography with flame thermionic detector and mass spectrometry. Statistical analysis using one-way ANOVA and Duncan's multiple range test (P < 0.05) was used to compare annual mean concentrations of pesticides, seasonal and spatial distribution. In general, the highest mean concentrations of the pesticides were recorded at the three stations downstream. The greatest average concentrations were determined during spring and summer in agreement with the pesticide application period. The observed lower concentrations after 2006 reflect the land-use change because of the elimination of tobacco, the main cultivation of the area for many decades. The compounds most frequently detected were diazinon (78.6%), DEA (69.3%), and fenthion (52.6%). Environmental risk assessment using risk quotient (RQ) approach showed high risk for six insecticides in 2005 and one in 2007. A compliance with the European Environmental Quality Standards (EQS) was observed for the priority pesticides.