The chemical composition of single particles deposited on industrial filters located in three different chimneys of an iron-manganese (Fe–Mn) alloy manufacturing plant have been compared using aerosol time-of-flight mass spectrometry (ATOFMS) and scanning electron microscopy–energy dispersive X-ray spectrometry (SEM-EDX). Very similar types of particles were observed using both analytical techniques. Calcium-containing particles dominated in the firing area of the sintering unit, Mn and/or Al-bearing particles were observed at the cooling area of the sintering unit, while Mn-containing particles were dominant at the smelting unit. SEM-EDX analysis of particles collected downstream of the industrial filters showed that the composition of the particles emitted from the chimneys is very similar to those collected on the filters. ATOFMS analysis of ore samples was also performed to identify particulate emissions that could be generated by wind erosion and manual activities. Specific particle types have been identified for each emission source (chimneys and ore piles) and can be used as tracers for source apportionment of ambient PM measured in the vicinity of the industrial site.

The growing use of lithium (Li) in industrial and energetic applications and the inability to completely recycle the alkali metal will most likely increase anthropogenic emissions and environmental concentrations in the future. Although non-essential to plants, Li+ is an important ultra-trace element in the animal and human diet and is also used in the treatment of e.g. mental disorders. Most of the lithium is consumed with the drinking water and vegetables, but concentrations in foodstuffs vary with the geochemistry of the element. In order to identify potential risks and to avoid an overmedication due to consumption of Li rich or Li contaminated foods it is advisable to identify background levels and to derive recommended Daily Allowances (RDAs) for the element. Although Germany does not possess large amounts of primary or secondary resources of lithium, geochemical investigations (mineral and ground waters and soils) in this country confirm a wide variation of environmental concentrations with generally higher levels in the southwest. Despite the large number of soil and water data, only very few data exist on lithium concentrations in plants and its phytotoxicity. Within the scope of present study common grassland plant species were sampled in regions of SW-Germany with reportedly high geogenic levels of Li. The data are discussed with regard to literature surveys and existing reference values. Since lithium has phytotoxic effects a greenhouse experiment was performed with different Li salts (LiCl and Li2CO3) and plant species (maize, bean and buckwheat) to derive dose-response relationships for the endpoint shoot growth. While corn growth was not reduced significantly by soil concentrations of 118 ppm, EC50 values in buckwheat were 47 and 16 ppm for lithium derived from LiCl and Li2CO3, respectively.

Estuarine environment is complex and receives different contaminants from numerous sources that are persistent, bioaccumulative and toxic. The distribution, source, contamination and ecological risk status of heavy metals in sediment of Brisbane River, Australia were investigated. Sediment samples were analysed for major and minor elements using LA-ICP-MS. Principal component analysis and cluster analysis identified three main sources of metals in the samples: marine sand intrusion, mixed lithogenic and sand intrusion as well as transport related. To overcome inherent deficiencies in using a single index, a range of sediment quality indices, including contamination factor, enrichment factor, index of geo-accumulation, modified degree of contamination, pollution index and modified pollution index were utilised to ascertain the sediment quality. Generally, the sediment is deemed to be “slightly” to “heavily” polluted. A further comparison with the Australian Sediment Quality Guidelines indicated that Ag, Cr, Cu, Ni, Pb and Zn had the potential to rarely cause biological effects while Hg could frequently cause biological effects. Application of potential ecological risk index (RI) revealed that the sediment poses moderate to considerable ecological risk. However, RI could not account for the complex sediment behaviour because it uses a simple contamination factor. Consequently, a modified ecological risk index (MRI) employing enrichment factor is proposed. This provides a more reliable understanding of whole sediment behaviour and classified the ecological risk of the sediment as moderate to very high. The results demonstrate the need for further investigation into heavy metal speciation and bioavailability in the sediment to ascertain the degree of toxicity.

The internal loading of P is reported to be the main factor initiating algal blooms. However, there are only a few reports on the dynamic variation of labile P in the sediment and overlying water during the decomposition of algal. In addition, the widely perceived relationship between labile P and Fe was not supported by in situ obtained values in freshwater. Consequently, the in situ simultaneous measurement of diffusion gradients in thin-film techniques (DGT) was applied on a large scale to detect the mechanisms of labile P and Fe in a typical shallow lake (Lake Hongze). The newly developed ZrO-DGT and ZrO-Chelex DGT were combined to obtain the concentration of labile P and Fe. Results showed that decomposition of algal might be the main contributor for the concentration dots and peaks of labile P in sediment profiles, as well as for the high values on the horizontal heterogeneity index of labile P at the depth of 0–30 mm of the sediment. Moreover, there existed significant difference between the apparent diffusion fluxes of labile P and Fe across the sediment–water interface which obtained from June sampling and October sampling. The results of apparent diffusion flux in two periods indicated the sediments changed from “sink” to “source” for labile P, especially at Sites 4–8, 10, 13–14, and 18. However, the role of the labile Fe has no significantly variation in the values of the diffusion flux. This phenomenon also contributed to the poor relationship between labile P and Fe in the sediment which obtained from the October sampling. Accordingly, we conclude that algal decomposition might be essential for internal loading of P in this aquatic ecosystem, and that also be the reason for vicious circle of algal occurrence in the following year in the center of Lake Hongze.

Freshwater ecosystems are threatened by multiple anthropogenic stressors, which might be differentiated into two types: those that reduce biological activity at all concentrations (toxic contaminants), and those that subsidize biological activity at low concentrations and reduce it at high concentrations (assimilable contaminants). When occurring in mixtures, these contaminants can have either antagonistic, neutral or synergistic effects; but little is known on their joint effects. We assessed the interaction effects of a mixture of assimilable and toxic contaminants on stream biofilms in a manipulative experiment using artificial streams, and following a factorial design with three nutrient levels (low, medium or high) and either presence or absence of a mixture of emerging contaminants (ciprofloxacin, erythromycin, diclofenac, methylparaben, and sulfamethoxazole). We measured biofilm biomass, basal fluorescence, gross primary production and community respiration. Our initial hypotheses were that biofilm biomass and activity would: increase with medium nutrient concentrations (subsidy effect), but decrease with high nutrient concentrations (stress effect) (i); decrease with emerging contaminants, with the minimum decrease at medium nutrient concentrations (antagonistic interaction between nutrients subsidy and stress by emerging contaminants) and the maximum decrease at high nutrient concentrations (synergistic interaction between nutrients and emerging contaminants stress) (ii). All the measured variables responded linearly to the available nutrients, with no toxic effect at high nutrient concentrations. Emerging contaminants only caused weak toxic effects in some of the measured variables, and only after 3–4 weeks of exposure. Therefore, only antagonistic interactions were observed between nutrients and emerging contaminants, as medium and high nutrient concentrations partly compensated the harmful effects of emerging contaminants during the first weeks of the experiment. Our results show that contaminants with a subsidy effect can alleviate the effects of toxic contaminants, and that long-term experiments are required to detect stress effects of emerging contaminants at environmentally relevant concentrations.

Coastal urban infrastructures are proliferating across the world, but knowledge about their emergent impacts is still limited. Here, we provide evidence that urban artificial reefs have a high potential to accumulate the diverse forms of litter originating from anthropogenic activities around cities. We test the hypothesis that the structural complexity of urban breakwaters, when compared with adjacent natural rocky intertidal habitats, is a driver of anthropogenic litter accumulation. We determined litter abundances at seven sites (cities) and estimated the structural complexity in both urban breakwaters and adjacent natural habitats from northern to central Chile, spanning a latitudinal gradient of ∼15° (18°S to 33°S). Anthropogenic litter density was significantly higher in coastal breakwaters when compared to natural habitats (∼15.1 items m−2 on artificial reefs versus 7.4 items m−2 in natural habitats) at all study sites, a pattern that was temporally persistent. Different litter categories were more abundant on the artificial reefs than in natural habitats, with local human population density and breakwater extension contributing to increase the probabilities of litter occurrence by ∼10%. In addition, structural complexity was about two-fold higher on artificial reefs, with anthropogenic litter density being highest at intermediate levels of structural complexity. Therefore, the spatial structure characteristic of artificial reefs seems to enhance anthropogenic litter accumulation, also leading to higher residence time and degradation potential. Our study highlights the interaction between coastal urban habitat modification by establishment of artificial reefs, and pollution. This emergent phenomenon is an important issue to be considered in future management plans and the engineering of coastal ecosystems.

In our earlier work, Tigriopus japonicus were subjected to different mercuric chloride treatments (0–50 μg/L in the seawater) for five generations (F0–F4), and they were subsequently resumed under clean environments for one generation, i.e., F5. Accumulative effects were hypothesized to participate in mercury (Hg) multigenerational toxicity, however phenotypic plasticity could be responsible for metal resistance in this copepod against the long term exposure. Here, we specifically investigated the proteome profiles in the F0, F2, and F5 copepods of the control and 50 μg/L metal treatment, respectively, so as to elucidate the action mechanisms for Hg toxicity/tolerance in T. japonicus under the long term exposure. Functional enrichment analysis showed that a quite different proteomic response was observed in F5 compared with F0 and F2. Namely, the vast majority of enrichments were correlated with the down-regulated proteins in F0 and F2, whereas the enrichments for F5 were mostly attributable to the up-regulated proteins, suggesting that different mechanisms are responsible for Hg toxicity and tolerance (i.e., phenotypic plasticity). Hg toxicity prohibited many proteins in F0 and F2 which are related to several critical processes/pathways, e.g., protein translation, macromolecule metabolic process, DNA replication, cell cycle, cuticle organization, vitellogenesis, etc. In F5, many up-regulated proteins were enriched into compensatory systems, such as carbohydrate metabolism, myosin reorganizations, and stress-related defense pathway. Notably, glycolysis (an oxygen-independent pathway) was enhanced for energy allocation into metal detoxification and tolerance. Taken together, proteomics provides novel mechanistic insights into phenotypic plasticity used by T. japonicus when challenged with cumulative effects due to Hg multigenerational toxicity.

As of November 2014, the Korean Ministry of Environment (KME) has been forecasting the concentration of particulate matter with diameters ≤ 10 μm (PM10) classified into four grades: low (PM10 ≤ 30 μg m−3), moderate (30 < PM10 ≤ 80 μg m−3), high (80 < PM10 ≤ 150 μg m−3), and very high (PM10 > 150 μg m−3). The KME operational center generates PM10 forecasts using statistical and chemistry-transport models, but the overall performance and the hit rate for the four PM10 grades has not previously been evaluated. To provide a statistical reference for the current air quality forecasting system, we have developed a neural network model based on the synoptic patterns of several meteorological fields such as geopotential height, air temperature, relative humidity, and wind. Hindcast of the four PM10 grades in Seoul, Korea was performed for the cold seasons (October–March) of 2001–2014 when the high and very high PM10 grades are frequently observed. Because synoptic patterns of the meteorological fields are distinctive for each PM10 grade, these fields were adopted and quantified as predictors in the form of cosine similarities to train the neural network model. Using these predictors in conjunction with the PM10 concentration in Seoul from the day before prediction as an additional predictor, an overall hit rate of 69% was achieved; the hit rates for the low, moderate, high, and very high PM10 grades were 33%, 83%, 45%, and 33%, respectively. Our findings also suggest that the synoptic patterns of meteorological variables are reliable predictors for the identification of the favorable conditions for each PM10 grade, as well as for the transboundary transport of PM10 from China. This evaluation of PM10 predictability can be reliably used as a statistical reference and further, complement to the current air quality forecasting system.

Concentration and spatial distribution of six phthalic acid esters (PAEs) and eight phenols in sediments of urban rivers, namely the Xi River (XR) and Pu River (PR) in Shenyang city, Northeast China were investigated and the ecological risk of these target pollutants was assessed based on the risk quotient (RQ) approach. Target PAEs and phenols were detected in most of sediment samples collected from the XR and PR. The concentrations of total PAEs in sediments varied from 22.4 to 369 μg/g dw in the XR and 3.71–46.9 μg/g dw in the PR. The levels of phenols ranged from 2.72 to 106 μg/g dw in the XR and 0.811–25.0 μg/g dw in the PR, respectively. The dominant pollutants in both XR and PR were DEHP, phenol and 4-methylphnol. The sampling locations XR1-3 in the XR suffered severe contamination from PAEs and phenols. The sites PR1 and PR6 were heavily polluted by phenols and PAEs, respectively. Almost all target PAEs and phenolic compounds in sediment of the XR exhibited medium or high ecological risk to organisms and the ecological risk in the PR mainly originated from PEAs, phenol and 4-methylphenol. These results would provide guidance for individual pollutant control and indicate that it is imperative to take some effective measures to reduce the pollution of those contaminants.

Manufactured nanoparticles (MNP) rapidly undergo aging processes once released from products. Silver sulfide (Ag2S) is the major transformation product formed during the wastewater treatment process for Ag-MNP. We examined toxicogenomic responses of pristine Ag-MNP, sulfidized Ag-MNP (sAg-MNP), and AgNO3 to a model soil organism, Caenorhabditis elegans. Transcriptomic profiling of nematodes which were exposed at the EC30 for reproduction for AgNO3, Ag-MNP, and sAg-MNP resulted in 571 differentially expressed genes. We independently verified expression of 4 genes (numr-1, rol-8, col-158, and grl-20) using qRT-PCR. Only 11% of differentially expressed genes were common among the three treatments. Gene ontology enrichment analysis also revealed that Ag-MNP and sAg-MNP had distinct toxicity mechanisms and did not share any of the biological processes. The processes most affected by Ag-MNP relate to metabolism, while those processes most affected by sAg-MNP relate to molting and the cuticle, and the most impacted processes for AgNO3 exposed nematodes was stress related. Additionally, as observed from qRT-PCR and mutant experiments, the responses to sAg-MNP were distinct from AgNO3 while some of the effects of pristine MNP were similar to AgNO3, suggesting that effects from Ag-MNP is partially due to dissolved silver ions.