Markus Sillanpää

Nanoadsorbents for Remediation of Aquatic Environment: Local and Practical Solutions for Global Water Pollution Problems

The authors present an overview with critical analysis of technical applicability of various nanoadsorbents such as carbon nanotubes, nano-zerovalent iron, and metal oxides–based and polymeric nanoparticles in treating contaminated water. To highlight their performance, selected information such as synthesis method, pH, dose required, pollutants concentrations, reaction time, and treatment efficiency is presented based on the literature survey of 276 articles (1989–2010). Their advantages and drawbacks in applications are evaluated. Nanoadsorbents that stand out for outstanding performance are compared to bulk activated carbon. The implications of nanoadsorbents to public health and their way forward for facilitating environmental sustainability are also discussed.

Behavior of titanium dioxide nanoparticles in Lemna minor growth test conditions

Titanium dioxide nanoparticles (TiO(2) NPs) have raised concern of environmental risks due to their widespread applications, but little is known about the potential toxicity of TiO(2) NPs to aquatic plants. The aim of this work was to study the effects of TiO(2) NPs on Lemna minor and to study the behavior of TiO(2) NPs under modified ISO 20079 test conditions. TiO(2) NPs had a tendency to aggregate in ISO (Steinberg) growth medium, but modification of the standard growth medium enabled the exposure of L. minor to TiO(2) NPs. By dilution of the growth medium (1:10), and exposure under semi-static conditions with medium renewal every second or third day, the size of TiO(2) particles remained rather stable throughout the test period. TiO(2) NPs showed no adverse effect on the growth rate or chlorophyll a content of L. minor, even at a high exposure concentration of 5 mg L(-1) and extended exposure time of 14 days. TiO(2) NPs attached onto L. minor cell walls, but no cellular uptake was observed. Although TiO(2) NPs were not toxic to L. minor, the potential transfer of TiO(2) NPs in aquatic food chains, e.g. attached to the plant leaves and other biological surfaces may be of importance, causing exposure of other organisms and contributing to the environmental fate of nanoparticles.

Aggregation and deposition of engineered TiO2 nanoparticles in natural fresh and brackish waters

The use and thus environmental release potential of metal-based nanoparticles have rapidly increased. Due to their size-dependent new properties, the fate and effect of nanomaterial may differ from those of the conventional form of corresponding material. The agglomeration and sedimentation were studied by spiking the TiO2-P25 particles in natural fresh and brackish water samples. The natural waters were determined for conductivity, pH, salinity, total organic carbon, turbidity, common nutrients and trace elements. The hydrodynamic diameter and concentration of TiO2-P25 particle dispersions were monitored by using a dynamic light scattering and a spectrophotometer, respectively. The experiments were performed at two particle concentrations 100 mg/l and 1 mg/l (10 mg/l for deposition studies). The aggregation rates in brackish waters were clearly higher in higher initial concentration and the sedimentation of aggregates decreased the TiO2 concentration down to 20% and 80% of initial higher and lower concentrations, respectively. One fresh water sample favoured the destabilisation of TiO2-P25 particles whereas another fresh water sample stabilised the TiO2 particle dispersion. The aggregation had a strong dependence on the particle concentration. High ionic content of brackish water probably explains the formation of aggregates, whereas organic substances and pH may account for the different agglomeration behaviour in fresh waters.

Estrogenic activity in Finnish municipal wastewater effluents.

Effluents from wastewater treatment plants (WWTPs) are a major source of estrogenic compounds to the aquatic environment. In the present work, estrogenic activities of effluents from eight municipal WWTPs in Finland were studied. The main objectives of the study were to quantify the concentrations of selected estrogenic compounds, to evaluate their contribution to estrogenic potency and to test the feasibility of the commercial bioassays for wastewater analysis. The effluent samples were analyzed by two in vitro tests, i.e. ERα-CALUX(®) and ELISA-E2, and by liquid chromatography mass spectrometry for six estrogenic compounds: estrone (E1), 17β-estradiol (E2), estriol (E3), 17α-ethinylestradiol (EE2), 17α-estradiol and bisphenol A (BPA). Estrogenic effects were found in all of the effluent samples with both of the bioassays. The concentrations measured with ELISA-E2 (8.6-61.6 ng/L) were clearly higher but exhibited a similar pattern than those with chemical analysis (E2 <limit of quantification - 6.8 ng/L) and ERα-CALUX(®) (0.8-29.7 ng E2 EEQ/L). Due to the concentrations under limit of quantification, the evaluation of the chemical contribution to estrogenic potency was possible only for E1 and BPA, which contributed less than 10% to the observed effects, except in one sample with a high BPA contribution (17%). The contribution of E2 was significant in two samples where it was detected (28% and 67%). The results demonstrated that more comprehensive information on potential estrogenic activity of wastewater effluents can be achieved by using in vitro biotests in addition to chemical analysis and their use would be beneficial in monitoring and screening purposes.

Occurrence, identification and removal of microplastic particles and fibers in conventional activated sludge process and advanced MBR technology

Wastewater treatment plants (WWTPs) are acting as routes of microplastics (MPs) to the environment, hence the urgent need to examine MPs in wastewaters and different types of sludge through sampling campaigns covering extended periods of time. In this study, the efficiency of a municipal WWTP to remove MPs from wastewater was studied by collecting wastewater and sludge samples once in every two weeks during a 3-month sampling campaign. The WWTP was operated based on the conventional activated sludge (CAS) process and a pilot-scale membrane bioreactor (MBR). The microplastic particles and fibers from both water and sludge samples were identified by using an optical microscope, Fourier Transform Infrared (FTIR) microscope and Raman microscope. Overall, the retention capacity of microplastics in the studied WWTP was found to be 98.3%. Most of the MP fraction was removed before the activated sludge process. The efficiency of an advanced membrane bioreactor (MBR) technology was also examined. The main related finding is that MBR permeate contained 0.4 MP/L in comparison with the final effluent of the CAS process (1.0 MP/L). According to this study, both microplastic fibers and particles are discharged from the WWTP to the aquatic environment.

Effect-based assessment of toxicity removal during wastewater treatment

Wastewaters contain complex mixtures of chemicals, which can cause adverse toxic effects in the receiving environment. In the present study, the toxicity removal during wastewater treatment at seven municipal wastewater treatment plants (WWTPs) was investigated using an effect-based approach. A battery of eight bioassays was applied comprising of cytotoxicity, genotoxicity, endocrine disruption and fish embryo toxicity assays. Human cell-based CALUX assays, transgenic larval models and the fish embryo toxicity test were particularly sensitive to WWTP effluents. The results indicate that most effects were significantly reduced or completely removed during wastewater treatment (76-100%), while embryo toxicity, estrogenic activity and thyroid disruption were still detectable in the effluents suggesting that some harmful substances remain after treatment. The responsiveness of the bioassays was compared and the human cell-based CALUX assays showed highest responsiveness in the samples. Additionally, the fish embryo toxicity test and the transgenic larval models for endocrine disrupting effects showed high responsiveness at low sample concentrations in nearly all of the effluent samples. The results showed a similar effect pattern among all WWTPs investigated, indicating that the wastewater composition could be rather similar at different locations. There were no considerable differences in the toxicity removal efficiencies of the treatment plants and no correlation was observed with WWTP characteristics, such as process configuration or sludge age. This study demonstrated that a biotest battery comprising of multiple endpoints can serve as a powerful tool when assessing water quality or water treatment efficiency in a holistic manner. Rather than analyzing the concentrations of a few selected chemicals, bioassays can be used to complement traditional methods of monitoring in the future by assessing sum-parameter based effects, such as mixture effects, and tackling chemicals that are present at concentrations below chemical analytical detection limits.