Cell size dependent toxicity thresholds of polycyclic aromatic hydrocarbons to natural and cultured phytoplankton populations

The toxicity of pyrene and phenanthrene to phytoplankton was studied by analyzing the effect on the growth, abundance and cell viability of cultured species and natural communities of the Atlantic Ocean and the Mediterranean Sea. A decrease in cell abundance, and growth rate was observed as concentration of PAHs increased, with catastrophic cell mortality induced at the highest PAH concentration tested. A strong positive linear relationship was observed between the LC50 (the PAH concentration at which cell population will decline by a half), and the species cell volume, for both phenanthrene and pyrene. Natural communities were however significantly more sensitive to PAHs than cultured phytoplankton, as indicated by the lower slope (e.g. 0.23 and 0.65, respectively, for pyrene) of the relationship LC50 vs. cell volume. The results highlight the importance of cell size in determining the phytoplankton sensitivity to PAHs identifying the communities from the oligotrophic ocean to be more vulnerable.     

Chemical and ecotoxicological analyses of sediments and elutriates of contaminated rivers due to e-waste recycling activities using a diverse battery of bioassays

A multi-trophic, multi-exposure phase assessment approach was applied to characterize the toxicity of sediments collected from two rivers in Guiyu, China, an e-waste recycling centre. Elutriate toxicity tests (bacterium Vibrio fischeri and microalga Selenastrum capricornutum) and whole sediment toxicity test (crustacean Heterocypris incongruens) showed that most sediments exhibited acute toxicity, due to elevated heavy metals and PAHs levels, and low pH caused by uncontrolled acid discharge. The survival rates of crustaceans were negatively (p < 0.05) correlated with total PAHs in sediments (411-1755 mg kg⁻¹); EC50s of V. fischeri on the elutriates were significantly correlated with elutriate pH (p < 0.01). Significant (p < 0.05) correlations between the induction of hepatic metallothionein in tilapia (Oreochromis mossambicus) and metal concentrations (Cu, Zn, Pb) in sediments were also observed, when fish were fed with diets containing sediment. The results showed that uncontrolled e-waste recycling activities may bring adverse effects to local aquatic ecosystem.     

Effect of birch (Betula spp.) and associated rhizoidal bacteria on the degradation of soil polyaromatic hydrocarbons, PAH-induced changes in birch proteome and bacterial community

Two birch clones originating from metal-contaminated sites were exposed for 3 months to soils (sand-peat ratio 1:1 or 4:1) spiked with a mixture of polyaromatic hydrocarbons (PAHs; anthracene, fluoranthene, phenanthrene, pyrene). PAH degradation differed between the two birch clones and also by the soil type. The statistically most significant elimination (p ≤ 0.01), i.e. 88% of total PAHs, was observed in the more sandy soil planted with birch, the clearest positive effect being found with Betula pubescens clone on phenanthrene. PAHs and soil composition had rather small effects on birch protein complement. Three proteins with clonal differences were identified: ferritin-like protein, auxin-induced protein and peroxidase. Differences in planted and non-planted soils were detected in bacterial communities by 16S rRNA T-RFLP, and the overall bacterial community structures were diverse. Even though both represent complex systems, trees and rhizoidal microbes in combination can provide interesting possibilities for bioremediation of PAH-polluted soils.     

Persistent organic pollutants in food items collected in Hong Kong

This study aims to investigate levels of POPs in meat, edible oils, nuts, milk and wine collected from Hong Kong. Naphthalene, pp-DDE, beta-, gamma-HCH and PBDE 47 were detected in most of the food items. Goose liver accumulated the highest PAHs (47.9 ng g⁻¹ wet wt), DDTs (25.6), HCHs (13.0), PCBs (4.17), PBDEs (468 pg g⁻¹ wet wt) among all the selected food. Meat and nut groups had significant (p < 0.01 or 0.05) correlations between lipid contents and concentrations of PAHs (meat: r = 0.878), HCHs (meat: r = 0.753), DDTs (meat: r = 0.937; nuts: r = 0.968) and PCBs (meat: r = 0.832; nut: r = 0.946). The concentrations of DDTs, HCHs and PCBs in vegetable oil were lower, but HCHs in fish oil were higher, when compared with other countries. The concentrations of PAHs, DDTs, PCBs and PBDEs in food tested in the present study were all below various safety guidelines.     

Estimation of the annual scavenged amount of polycyclic aromatic hydrocarbons by forests in the Pearl River Delta of Southern China

Leaves of six main tree species from the Pearl River Delta (PRD) in Southern China were collected to identify the interspecific variability, the spatial variability and the seasonal variations of polycyclic aromatic hydrocarbons' (PAHs) concentrations, and to calculate the amount of PAHs removed by leaves. PAHs concentrations in pine needles were much higher than in broad-leaves and leaves from urban/industrial areas (Baiyunshan and Heshan) exhibited two times greater concentrations than leaves from the rural area (Dinghushan). Seasonal variations of PAHs in leaves occurred with lesser concentrations in September. Leaves in PRD scavenged 3.7 ± 0.9 t PAHs y⁻¹, accounting for about 10% of the total amount emitted in this region. This result suggests that forests play an important role in the fate of PAHs.     

Predicting bioavailability of PAHs in field-contaminated soils by passive sampling with triolein embedded cellulose acetate membranes

Triolein embedded cellulose acetate membrane (TECAM) was used for passive sampling of the fraction of naphthalene, phenanthrene, pyrene and benzo[a]pyrene in 18 field-contaminated soils. The sampling process of PAHs by TECAM fitted well with a first-order kinetics model and PAHs reached 95% of equilibrium in TECAM within 20 h. Concentrations of PAHs in TECAM (C_TECAM) correlated well with the concentrations in soils (r² = 0.693-0.962, p < 0.001). Furthermore, concentrations of PAHs determined in the soil solution were very close to the values estimated by C_TECAM and the partition coefficient between TECAM and water (K_TECAM-w). After lipid normalization nearly 1:1 relationships were observed between PAH concentrations in TECAMs and earthworms exposed to the soils (r² = 0.591-0.824, n = 18, p < 0.01). These results suggest that TECAM can be a useful tool to predict bioavailability of PAHs in field-contaminated soils.     

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag–Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag–PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72 h in freshwater (500–600 μg L⁻¹) and seawater (1300–1500 μg L⁻¹), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag⁺ (1.1, 400 and 0.11 μg L⁻¹, respectively), Ag–Cit (3.0, 2380 and 0.15 μg L⁻¹, respectively) and Ag–PVP (19.5, 3690 and 2.0 μg L⁻¹, respectively) varied widely, with toxicity in the order Ag⁺ > Ag–Cit > Ag–PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag⁺ or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.     

Microbial degradation of pharmaceuticals in estuarine and coastal seawater

Microbial degradation rates were measured for 19 pharmaceuticals in estuarine and coastal surface water samples. Antipyrine, carbamazepine, cotinine, sulfamethoxazole, and trimethoprim were the most refractory (half-lives, t_1/2 = 35 to >100 days), making them excellent candidates for wastewater tracers. Nicotine, acetaminophen, and fluoxetine were labile across all treatments (t_1/2 = 0.68-11 days). Caffeine, diltiazem, and nifedipine were also and relatively labile in all but one of the treatments (t_1/2 = 3.5-13 days). Microbial degradation of caffeine was further confirmed by production ¹⁴CO₂. The fastest decay of non-refractory compounds was always observed in more sewage-affected Jamaica Bay waters. Degradation rates for the majority of these pharmaceuticals are much slower than reported rates for small biomolecules, such as glucose and amino acids. Batch sorption experiments indicate that removal of these soluble pharmaceuticals from the water column to sediments is a relatively insignificant removal process in these receiving waters.     

PM(10)-bound polycyclic aromatic hydrocarbons: biological indicators, lung cancer risk of realistic receptors and 'source-exposure-effect relationship' under different source scenarios

Cancer has become a critical health issue in the world heritage city Kandy, Sri Lanka. Polycyclic aromatic hydrocarbons (PAHs), one of persistent organic pollutants, in the atmosphere may be a major etiological factor in lung carcinogenicity. Over the very high concentrations of ambient air PAHs reported in Kandy, this paper is focused on setting priorities to control human exposure to PAHs in prevention of cancer.On re-appraisal of the classical indicator benzo(a)pyrene (B[a]P) for atmospheric PAHs-related carcinogenicity, B[a]P failed to reflect the toxicity completely and may not be the sole indicator for risk assessment studies in complex multi-sourced urban environments. The excess lifetime lung cancer risks of atmospheric PAHs with ‘less than lifetime exposure’ were assessed based on both ‘B[a]P toxic equivalents’ and ‘B[a]P surrogate epidemiological’ approach of risk quantification, over emissions characterized urban, suburban, and rural areas of Kandy. In urban heavy traffic areas, PAH-related additional cancer burden has been 942 million⁻¹ over 30 y of exposure. Over the whole study area, ∑p-PAHs show strong correlation (r = 0.8) to the predicted risk levels. While the urban and suburban predicted cancer risk levels could not show significant correlation to their emission sources indicating the real complexity in mega urban environments, the rural lung cancer risk levels correlated perfectly with the source, firewood combustion.Policy decisions on environment and health could be based on established correlations among ‘emission sources-exposures-health effects’. The priority for “analysis of options and policy formulation to reduce inhalation PAHs exposure of population in Kandy” was considered “moderate to high”.     

Black carbon (BC) in urban and surrounding rural soils of Beijing, China: spatial distribution and relationship with polycyclic aromatic hydrocarbons (PAHs)

The concentrations of black carbon (BC), total organic carbon (TOC) and polycyclic aromatic hydrocarbons (PAHs) have been determined in soils from urban and rural areas of Beijing. The rural area can be divided into plain and mountainous areas which are close to and relatively far from the urban area, respectively. Concentration of BC (5.83 ± 3.05 mg g⁻¹) and BC/TOC concentration ratio (0.37 ± 0.15) in Beijing’s urban soil are high compared with that in world background soils and rural soils of Beijing, suggesting the urban environment to be an essential source and sink of BC. Concentration of BC in the urban area decreases from the inner city to exterior areas, which correlates with the urbanization history of Beijing and infers accumulation of BC in old urban soils. Black carbon in Beijing soils mainly comes from fossil fuel combustion, especially traffic emission. Median PAH concentration in the urban area (502 ng g⁻¹) is one order of magnitude higher than that in the rural plain (148 ng g⁻¹) and mountainous area (146 ng g⁻¹) where PAHs are supposed to mainly come from atmospheric deposition from the urban area. Concentrations of BC correlate significantly with those of PAHs (p < 0.01, except naphthalene) in the urban area and with those of heavier 4-, 5- and 6- ring PAHs (p < 0.01) in the adjacent rural plain area, while there is no significant correlation with any PAH in the farther rural mountainous area.     

Assessing the toxicity of sodium chloride to the glochidia of freshwater mussels: implications for salinization of surface waters

Chloride concentrations in surface waters have increased significantly, a rise attributed to road salt use. In Canada, this may be a concern for endangered freshwater mussels, many with ranges limited to southern Ontario, Canada’s most road-dense region. The acute toxicity of NaCl was determined for glochidia, the mussel’s larval stage. The 24 h EC50s of four (including two Canadian endangered) species ranged from 113-1430 mg Cl L⁻¹ (reconstituted water, 100 mg CaCO₃ L⁻¹). To determine how mussels would respond to a chloride pulse, natural river water (hardness 278-322 mg CaCO₃ L⁻¹) was augmented with salt. Lampsilis fasciola glochidia were significantly less sensitive to salt in natural water (EC50s 1265-1559 mg Cl L⁻¹) than in reconstituted water (EC50 285 mg L⁻¹). Chloride data from mussel habitats revealed chloride reaches levels acutely toxic to glochidia (1300 mg L⁻¹). The increased salinization of freshwater could negatively impact freshwater mussels, including numerous species at risk.     

Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) in urban soils of Bratislava, Slovakia: patterns, relation to PAHs and vertical distribution

We determined concentrations, sources, and vertical distribution of OPAHs and PAHs in soils of Bratislava. The ∑14 OPAHs concentrations in surface soil horizons ranged 88-2692 ng g⁻¹ and those of ∑34 PAHs 842-244,870 ng g⁻¹. The concentrations of the ∑9 carbonyl-OPAHs (r = 0.92, p = 0.0001) and the ∑5 hydroxyl-OPAHs (r = 0.73, p = 0.01) correlated significantly with ∑34 PAHs concentrations indicating the close association of OPAHs with parent-PAHs. OPAHs were quantitatively dominated by 9-fluorenone, 9,10-anthraquinone, 1-indanone and benzo[a]anthracene-7,12-dione. At several sites, individual carbonyl-OPAHs had higher concentrations than parent PAHs. The concentration ratios of several OPAHs to their parent-PAHs and contribution of the more soluble OPAHs (1-indanone and 9-fluorenone) to ∑14 OPAHs concentrations increased with soil depth suggesting that OPAHs were faster vertically transported in the study soils by leaching than PAHs which was supported by the correlation of subsoil:surface soil ratios of OPAH concentrations at several sites with K_OW.     

Impact of atmospheric deposition of anthropogenic and natural trace metals on Northwestern Mediterranean surface waters: a box model assessment

Under stratified oligotrophic conditions (May-November), the surface mixed layer of the Northwestern Mediterranean constitutes a homogeneous water volume of 10-30 m depth. In other respects, the mean residence time of Ligurian surface waters (0-200 m) is 102 days. It is therefore possible to quantify the extent to which atmospheric deposition of trace metals affects surface waters. On the basis of literature data on anthropogenic and natural trace metals, we demonstrate that the ratios between total seawater labile atmospheric deposition during 102 days (Δc) and dissolved TM concentrations in Ligurian surface waters (c) illustrate the impact of atmospheric deposition on surface seawater (Δc/c). High ratios indicate surface TM enrichments, while low ratios indicate surface TM depletion, due to the quasi-complete sorption and removal of TMs by plankton during spring bloom. The simple box model proposed here may be used for other marine regions where hydrodynamical and physico-chemical constraints are well defined.     

Relationships between organic matter, black carbon and persistent organic pollutants in European background soils: Implications for sources and environmental fate

Black carbon (BC) and total organic carbon (TOC) contents of UK and Norwegian background soils were determined and their relationships with persistent organic pollutants (HCB, PAHs, PCBs, co-planar PCBs, PBDEs and PCDD/Fs) investigated by correlation and regression analyses, to assess their roles in influencing compound partitioning/retention in soils. The 52 soils used were high in TOC (range 54-460 mg/g (mean 256)), while BC only constituted 0.24-1.8% (0.88%) of the TOC. TOC was strongly correlated (p < 0.001) with HCB, PCBs, co-PCBs and PBDEs, but less so with PCDD/Fs (p < 0.05) and PAHs. TOC explained variability in soil content, as follows: HCB, 80%; PCBs, 44%; co-PCBs, 40%; PBDEs, 27%. BC also gave statistically significant correlations with PBDEs (p < 0.001), co-PCBs (p < 0.01) and PCBs, HCB, PCDD/F (p < 0.05); TOC and BC were correlated with each other (p < 0.01). Inferences are made about possible combustion-derived sources, atmospheric transport and air-surface exchange processes for these compounds.     

Bioavailability of residual polycyclic aromatic hydrocarbons following enhanced natural attenuation of creosote-contaminated soil

The impact of residual PAHs (2250 ± 71 μg total PAHs g⁻¹) following enhanced natural attenuation (ENA) of creosote-contaminated soil (7767 ± 1286 μg total PAHs g⁻¹) was assessed using a variety of ecological assays. Microtox™ results for aqueous soil extracts indicated that there was no significant difference in EC₅₀ values for uncontaminated, pre- and post-remediated soil. However, in studies conducted with Eisenia fetida, PAH bioaccumulation was reduced by up to 6.5-fold as a result of ENA. Similarly, Beta vulgaris L. biomass yields were increased 2.1-fold following ENA of creosote-contaminated soil. While earthworm and plant assays indicated that PAH bioavailability was reduced following ENA, the residual PAH fraction still exerted toxicological impacts on both receptors. Results from this study highlight that residual PAHs following ENA (presumably non-bioavailable to bioremediation) may still be bioavailable to important receptor organisms such as earthworms and plants.     

Impact of different land uses on polycyclic aromatic hydrocarbon contamination in coastal stream sediments

PAHs are ubiquitous environmental pollutants that can cause adverse health and ecological effects. In the present study, we examined the impact of land use on the concentration and composition of PAHs in 28 coastal stream sediments on the Island of Oahu, Hawaii. In densely populated urban areas, the concentration range of total PAHs in the stream sediments affected by mixed residential and industrial activities (RI) are 0.40-9.05 ppm, which is significantly higher than the 0.36-4.21 ppm detected in the stream sediments affected predominantly by urban residential land uses (UR). The stream sediments affected by agricultural activities (AG) reported a concentration range of 0.09-2.14 ppm, which is lower than those of the RI and UR stream sediments. The molecular weight of PAH is a factor, as only high molecular weight (HMW) PAHs were significantly affected by land uses (ANOVA P = 0.009). Correlation analysis showed that only in the UR stream sediments were significant correlations observed between PAH concentration and two anthropogenic indicators: population density (r = 0.57, P = 0.027) and vehicle density (r = 0.55, P = 0.034). The fractional concentrations of PAHs were analyzed by using PCA analysis, which led to the separate clustering of the RI and AG stream sediments and suggest distinct PAH sources between the two land uses. Two PAH source indicators, including Ant/(Ant + Phe) and Fl/(Fl + Py), indicates that PAHs sources in the RI stream sediments are most likely of petroleum origin, while PAHs in the UR and AG stream sediments most likely came from combustion activities. In addition, the concentration and relative potency of carcinogenic PAHs in the coastal stream sediments exhibited similar patterns as the total PAH concentration with respect to land uses.     

Phytoplankton toxicity of the antibiotic chlortetracycline and its UV light degradation products

Two common freshwater phytoplankton species Microcystis aeruginosa and Scenedesmus obliquus were employed as test organisms to investigate the toxic effects of chlortetracycline widely used in human medicine and veterinary as antibiotic. Toxicity assays were performed into two parts: antibiotic toxicity test and antibiotic degraded products toxicity test. In general, chlortetracycline had significantly toxic effect on population growth and chlorophyll-a accumulation of two phytoplankton. Although M. aeruginosa had ability to grow after exposed to chlortetracycline at 0.5 mg L⁻¹, its photosynthesis function was also disrupted. Compared with the data in two phytoplankton species, the chlorophyceae was more sensitive than the cyanophyceae. The adverse effect on S. obliquus was stronger than that on M. aeruginosa with increasing concentrations. In addition, for M. aeruginosa, regardless of the UV light degradation time, the treated chlortetracycline also had adverse effect on population growth and chlorophyll-a accumulated. The degraded chlortetracycline under any treatment time was more toxic for S. obliquus than chlortetracycline itself excluding under 24 h. However, the correlation between the toxicity and degradation time was not clear and toxicity enhanced in fact did not follow the increase or decrease in degradation time. Our study showed that the antibiotic chlortetracycline and its degraded products had adverse effect on freshwater phytoplankton, the former has not been reported before and the latter has been overlooked in other research in the past.     

Distribution of PAHs in tissues of wetland plants and the surrounding sediments in the Chongming wetland, Shanghai, China

Polycyclic aromatic hydrocarbons (PAHs) concentrations were determined in sediments and three types of wetland plants collected from the intertidal flats in the Chongming wetland. The concentration of total PAHs in sediments ranged from 38.7 to 136.2 ng g⁻¹. Surface sediment concentrations were higher in regions with plant cover than in bare regions. Rhizome-layer sediments (56.8-102.4 ng g⁻¹) contained less PAHs than surface sediments (0-5 cm). Concentrations of PAHs in plant tissues ranged from 51.9 to 181.2 ng g⁻¹, with highest concentrations in the leaves of Scirpus. Most of the PAHs in the leaves and other plant tissues were low molecular weight compounds (LMW, 2-4 rings), and a similar distribution pattern of PAHs in different types of plants was also observed. Source analysis indicated that plants and sediments both came from pyrogenic sources, but plants had additional petroleum contamination. The low ratio of benzo[a]anthracene over chrysene suggests that the wetland PAHs came mainly from long-distance atmospheric transportation. Significant bioaccumulation of PAHs from the sediments into plants was not observed for high molecular weight PAHs (HMW, 5-6 rings) in Chongming wetland. The small RCFs (root concentration factor from sediments) for HMW PAHs and large RCFs for LMW PAHs suggested that roots accumulated LMW PAHs selectively from sediments in Chongming wetland.     

Use of thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) on identification of odorant emission focus by volatile organic compounds characterisation

Volatile organic compounds (VOCs) from several different municipal solid wastes’ treatment plants in Mallorca (Spain) have been analysed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Ambient (immission) air was collected during February and March 2011 by active sampling onto sorbents Tenax™ TA and Carboxen™ 1000. The study presents the chemical characterisation of 93 volatile organic compounds (VOCs) from an overall set of 84 immission air samples. 70 VOCs were positively identified.The linear fit for all 93 external standard calibration, from 10 mg L⁻¹ to 150 mg L⁻¹ (n = 4), was within the range 0.974 < r² < 0.998. Limits of detection of the method (LOD) for all the standards were within the range 1.1-4,213 pg, as the absolute standard amount spiked into sorbent tubes in 1 μL standard mixture (dissolved in methanol).Overall results stated systematic correlation between waste’s nature and VOCs’ air composition. Organic wastes show main contribution of terpenes, waste water sludge residues’ of reduced sulphured compounds (RSCs) and municipal solid wastes show contribution of a wide sort of VOCs. The use of a chemometric approach for variable’s reduction to 12 principal components enables evaluation of similarities and dissimilarities between facilities. PCA clearly related samples to its corresponding facility on the basis of their VOCs composition and the ambient temperature.     

Comparative phototoxicity of nanoparticulate and bulk ZnO to a free-living nematode Caenorhabditis elegans: the importance of illumination mode and primary particle size

The present study evaluated phototoxicity of nanoparticulate ZnO and bulk-ZnO under natural sunlight (NSL) versus ambient artificial laboratory light (AALL) illumination to a free-living nematode Caenorhabditis elegans. Phototoxicity of nano-ZnO and bulk-ZnO was largely dependent on illumination method as 2-h exposure under NSL caused significantly greater mortality in C. elegans than under AALL. This phototoxicity was closely related to photocatalytic reactive oxygen species (ROS) generation by the ZnO particles as indicated by concomitant methylene blue photodegradation. Both materials caused mortality in C. elegans under AALL during 24-h exposure although neither degraded methylene blue, suggesting mechanisms of toxicity other than photocatalytic ROS generation were involved. Particle dissolution of ZnO did not appear to play an important role in the toxicity observed in this study. Nano-ZnO showed greater phototoxicity than bulk-ZnO despite their similar size of aggregates, suggesting primary particle size is more important than aggregate size in determining phototoxicity.