Microcystins are cyanobacterial hepatotoxins capable of accumulation into animal tissues. The toxins act by inhibiting specific protein phosphatases and both non-covalent and covalent interactions occur. The 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) method determines the total, i.e. the sum of free and protein-bound microcystin in tissues. The aim of the method development in this paper was to tackle the problems with the MMPB methodology: the rather laborious workflow and the loss of material during different steps of the method. In the optimised workflow the oxidation recovery was of acceptable level (29–40%), the extraction efficiency good (62–97%), but the signal suppression effect from the matrix remained severe in our system (16–37% signal left). The extraction efficiency for the determination of the free, extractable microcystins, was found to be good, 52–100%, depending on the sample and the toxin variant and concentration. The study concerns method development for the LC–MS–MS analysis of both free and protein-bound microcystin in tissue materials.

Laboratory batch and column experiments were conducted to investigate the immobilization of phosphorus (P) in soils using synthetic magnetite nanoparticles stabilized with sodium carboxymethyl cellulose (CMC-NP). Although CMC-stabilized magnetite particles were at the nanoscale, phosphorus removal by the nanoparticles was less than that of microparticles (MP) without the stabilizer due to the reduced P reactivity caused by the coating. The P reactivity of CMC-NP was effectively recovered when cellulase was added to degrade the coating. For subsurface non-point P pollution control for a water pond, it is possible to inject CMC-NP to form an enclosed protection wall in the surrounding soils. Non-stabilized “nanomagnetite” could not pass through the soil column under gravity because it quickly agglomerated into microparticles. The immobilized P was 30% in the control soil column, 33% when treated by non-stabilized MP, 45% when treated by CMC-NP, and 73% when treated by both CMC-NP and cellulase. CMC-stabilized magnetite nanoparticles can effectively penetrate soil columns and immobilize phosphate in situ.

A comprehensive evaluation of organic contamination was performed in sediments sampled in two reference and three impacted small streams where endocrine disruptive (ED) effects in fish have been evidenced. The approach combined quantitative chemical analyses of more than 50 ED chemicals (EDCs) and a battery of in vitro bioassays allowing the quantification of receptor-mediated activities, namely estrogen (ER), androgen (AR), dioxin (AhR) and pregnane X (PXR) receptors. At the most impacted sites, chemical analyses showed the presence of natural estrogens, organochlorine pesticides, parabens, polycyclic aromatic hydrocarbons (16 PAHs), bisphenol A and alkylphenols, while synthetic steroids, myco-estrogens and phyto-estrogens were not detected. Determination of toxic-equivalent amounts showed that 28–96% of estrogenic activities in bioassays (0.2–6.3 ng/g 17β-estradiol equivalents) were explained by 17β-estradiol and estrone. PAHs were major contributors (20–60%) to the total dioxin-like activities. Interestingly, high PXR and (anti)AR activities were detected; however, the targeted analysed compounds could not explain the measured biological activities. This study highlighted the presence of multiple organic EDCs in French river sediments subjected to mixed diffuse pollution, and argues for the need to further identify AR and PXR active compounds in the aquatic environment. Multiple endocrine disrupting chemicals (ER, AR, AhR and PXR ligands) are detected in French river sediments using a panel of in vitro bioassays and analytical methods.

Palladium/magnetite nanoparticulate catalysts were developed for efficient elimination of halogenated organic pollutants from contaminated wastewater. Particle recovery from treated water can be ensured via magnetic separation. However, in worst-case scenarios, this catalyst removal step might fail, leading to particle release into the environment. Therefore, a toxicological study was conducted to investigate the impact of both pure magnetite and palladium/magnetite nanoparticle exposure upon human skin (HaCaT) and human colon (CaCo-2) cell lines and a cell line from rainbow trout gills (RTgill-W1). To quantify cell viability after particle exposure, three endpoints were examined for all tested cell lines. Additionally, the formation of reactive oxygen species was studied for the human cells. The results showed only minor effects of the particles on the tested cell systems and support the assumption that palladium/magnetite nano-catalysts can be implemented for a new wastewater treatment technology in which advantageous catalyst properties outweigh the risks. Impact of nano-Pd/magnetite on cell viability was studied and appears to be low.

Chars were generated by pyrolyzing pine wood at temperatures between 300 °C and 700 °C for 6 h and at 500 °C for 10–300 min. Their organic content and surface acidity decreased, and BET surface area increased, with increasing pyrolytic temperature and time. The uptake of benzene and nitrobenzene increased with increasing pyrolytic temperature and time with isotherms characterized by a transition from less to more concave-downward. The isotherms with low-temperature and short-time chars were fitted to the dual Langmuir-partition model, whereas those with high-temperature chars to the dual-Langmuir model. Calculations suggest that the organic phases of chars functioned as partition media and the uptake of benzene and nitrobenzene on carbonized chars occurred first in micropores via pore-filling and later in larger pores through capillary condensation and adsorption. It is concluded that chars may be considered to consist of the partition domain, the high-energy micropores domain and the low-energy large pores domain. Pine chars consist of the partition domain, the micropores domain and the large pores domain in terms of organic contaminant uptake.

In an extensive environmental study, field samples, including soil, water, rice, vegetable, fish, human hair and urine, were collected at an abandoned tungsten mine in Shantou City, southern China. Results showed that arsenic (As) concentration in agricultural soils ranged from 3.5 to 935 mg kg−1 with the mean value of 129 mg kg−1. In addition, As concentration reached up to 325 μg L−1 in the groundwater, and the maximum As concentration in local food were 1.09, 2.38 and 0.60 mg kg−1 for brown rice, vegetable and fish samples, respectively, suggesting the local water resource and food have been severely contaminated with As. Health impact monitoring data revealed that As concentrations in hair and urine samples were up to 2.92 mg kg−1 and 164 μg L−1, respectively, indicating a potential health risk among the local residents. Effective measurements should be implemented to protect the local community from the As contamination in the environment. It is the first report on arsenic contamination and potential health risk implications at abandoned Lianhuashan tungsten mine.

The effects of various factors including turbidity, pH, DOC, temperature, and solar radiation on the concentrations of total mercury (TM) and dissolved gaseous mercury (DGM) were investigated in an artificial reservoir in Korea. Episodic total mercury accumulation events occurred during the rainy season as turbidity increased, indicating that the TM concentration was not controlled by direct atmospheric deposition. The DGM concentration in surface water ranged from 3.6 to 160 pg/L, having a maximum in summer and minimum in winter. While in most previous studies DGM was controlled primarily by a photo-reduction process, DGM concentrations tracked the amount of solar radiation only in winter when the water temperature was fairly low in this study. During the other seasons microbial transformation seemed to play an important role in reducing Hg(II) to Hg(0). DGM increased as dissolved organic carbon (DOC) concentration increased (p-value < 0.01) while it increased with a decrease of pH (p-value < 0.01). Long-term in-situ monitoring of TM and DGM concentrations with various factors was executed in a large artificial reservoir in this study.

Anthropogenic trace element emissions have declined. However, top soils all over the world remain enriched in trace elements. We investigated Pb and Cd migration in forest soils of a remote monitoring site in the Austrian limestone Alps between 1992 and 2004. Large spatial variability masked temporal changes in the mineral soil of Lithic Leptosols (Skeltic), whereas a significant reduction of Pb concentrations in their forest floors occurred. Reductions of concentrations in the less heterogeneous Cambisols (Chromic) were significant. In contrast, virtually no migration of Pb and Cd were found in Stagnosols due to their impeded drainage. Very low element concentrations (<1 μg l−1) in field-collected soil solutions using tension lysimeters (0.2 μm nylon filters) imply that migration largely occurred by preferential flow as particulate-bound species during intensive rainfall events. Our results indicate that the extent of Pb and Cd migration in soils is largely influenced by soil type. Comparison between soil solid phase and soil solution concentrations imply that trace element migration largely occurred by preferential flow as particulate-bound species.

The present study addresses the key issue of linking the chemical speciation to the uptake of priority pollutants Cd(II) and Pb(II) in the wastewater treatment plant effluents, with emphasis on the role of the colloidal organic matter (EfOM). Binding of Cd(II) and Pb(II) by EfOM was examined by an ion exchange technique and flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry in parallel to bioassays with green microalga Chlorella kesslerii in ultrafiltrate (<1 kDa) and colloidal isolates (1 kDa to 0.45 μm). The uptake of Cd by C. kesslerii was consistent with the speciation analysis and measured free metal ion concentrations, while Pb uptake was much greater than that expected from the speciation measurement. Better understanding of the differences in the effects of the EfOM on Cd(II) and Pb(II) uptake required to take into account the size dependence of metal binding by EfOM. Colloids isolated from WWTP effluents decrease Cd uptake, but increase Pb uptake by microalga Chlorella kesslerii.