Alkylphenolic compounds and bisphenol A contamination within a heavily urbanized area: case study of Paris

This study evaluates the influence of a heavily urbanized area (Paris Metropolitan area), on receiving water contamination by both bisphenol A (BPA) and alkylphenol ethoxylate (APE) biodegradation product. The study began by investigating concentrations within urban sources. In addition to the more commonly studied wastewater treatment plant effluent, wet weather urban sources (including combined sewer overflows, urban runoff, and total atmospheric fallout) were considered. The initial results highlight a significant contamination of all urban sources (from a few nanograms per liter in atmospheric fallout to several micrograms per liter in the other sources) with clearly distinguishable distribution patterns. Secondly, concentration changes along the Seine River from upstream of the Paris Metropolitan area to downstream were investigated. While the concentrations of BPA and nonylphenoxy acetic acid (NP₁EC) increase substantially due to urban sources, the 4-nonylphenol concentrations remain homogeneous along the Seine. These results suggest a broad dissemination of 4-nonylphenol at the scale of the Seine River basin. Moreover, the relationship between pollutant concentrations and Seine River flow was assessed both upstream and downstream of the Paris conurbation. Consequently, a sharp decrease in dissolved NP₁EC concentrations relative to Seine River flow underscores the influence of single-point urban pollution on Seine River contamination. Conversely, dissolved 4-nonylphenol concentrations serve to reinforce the hypothesis of its widespread presence at the Seine River basin scale.     

Applying physicochemical approaches to control phosphogypsum heavy metal releases in aquatic environment

One of the most important sources of solid waste in the Mediterranean Basin ecosystem originated from the phosphate fertilizer industries, which discharge phosphogypsum (PG) directly into aquatic environments or are stacked on stockpiles. The present study investigates metal release from PG under the influence of variable pH, increasing PG mass content, and complexing organic matter ligands. Major ions from PG leachates, grain size and charge, main functional groups along with metal leachability (Pb, Cd, Cr, Cu, and Zn) were determined using ion chromatography, laser diffraction, zetameter, Fourier transform infrared spectroscopy, and atomic absorption spectroscopy, respectively. The complete dissolution of PG recorded is at 2 g/L. Saturation and supersaturation with respect to PG may occur at concentrations of 3 and 4 g/L, respectively, revealing a clustering phenomenon leading to heavy metal encapsulation within the aggregates. Organic ligands such as citrate may trigger the cationic exchange within the PG suspension leading to ion release. As these factors are considered as specific process involving the release of contaminants from PG during storage under natural conditions, this study could set the foundations for PG remediation in aquatic environment. Organic ligands under controlled pH conditions could be utilized in treating fertilizer industrial wastes by taking into consideration the particularity of the receiving area, thus decreasing metal hazardous impact on natural media.     

Occurrence of PCDD/Fs and dioxin-like PCBs in superficial sediment of Portuguese estuaries

Superficial sediments collected from seven estuarine systems located along the Portuguese coast were analyzed for 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs). Total PCDD/F concentration ranged from 4.6 to 464 pg g^?1 dry weight (dw), while that of dl-PCBs varied from 26.6 to 8,693 pg g^?1 dw. In general, the highest PCDD/F and dl-PCB concentrations were associated with densely populated and industrially impacted areas. Additionally, PCDD/F revealed a predominance of octachlorodibenzodioxin (OCDD) to total PCDD/Fs, while PCB 118 was the major contributor to total dl-PCBs. This study provided a global perspective of the contamination status of Portuguese estuaries by dioxin-like compounds and allowed a comparison between the investigated systems and other systems worldwide. PCDD/F and dl-PCB levels found in the collected sediments were lower than those of highly impacted areas from different parts of the globe. Nevertheless, comparison with guidelines and quality standards from other countries indicated that some Portuguese estuarine areas with a high industrialization level present PCDD/F and dl-PCB concentrations in superficial sediment that may constitute a risk to aquatic organisms.     

Effects of chronic exposure to lead,copper, zinc,and cadmium on biomarkers of the European eel,Anguilla anguilla

Exposure to specific metallic compounds can cause severe deleterious modifications in organisms. Fishes are particularly prone to toxic effects from exposure to metallic compounds via their environment. Species that inhabit estuaries or freshwater environments can be chronically affected by persistent exposure to a large number of metallic compounds, particularly those released by industrial activities. In this study, we exposed yellow eels (European eel, Anguilla anguilla) for 28 days to environmentally relevant concentrations of four specific metals; lead (300, 600, and 1,200 μg/l), copper (40, 120, and 360 μg/l), zinc (30, 60, and 120 μg/l) and cadmium (50, 150, and 450 μg/l). The selected endpoints to assess the toxicological effects were neurotransmission (cholinesterasic activity in nervous tissue), antioxidant defense, and phase II metabolism (glutathione-S-transferase [GST] activity, in both gills and liver tissues), and peroxidative damage. The results showed an overall lack of effects on acetylcholinesterase for all tested metals. Lead, copper, and cadmium exposure caused a significant, dose-dependent, increase in GST activity in gill tissue. However, liver GST only significantly increased following zinc exposure. No statistically significant effects were observed for the thiobarbituric acid reactive substances assay, indicating the absence of peroxidative damage. These findings suggest that, despite the occurrence of an oxidative-based response after exposure to lead, copper, and cadmium, this had no consequence in terms of peroxidative membrane damage; furthermore, cholinergic neurotoxicity caused by lead, copper, and cadmium did not occur. The implications of these results are further discussed.     

Assessment of heavy metal and organic contaminants levels along the Libyan coast using transplanted mussels (Mytilus galloprovincialis)

Within the framework of the MYTIOR project in 2009, heavy metals and organic compounds contaminations were assessed in transplanted mussels in 16 different stations along the coasts of Libya. These stations were located at miles offshore industrial/urban sources but in open sea providing original results related to the background contamination rather than linked to a specific coastal source of pollutants. Results indicated mercury (Hg, 0.045–0.066 mg/kg dry weight (dw)), lead (Pb, 0.44–0, 71 mg/kg dw) and copper (Cu, 3.56–4.21 mg/kg dw) were in the same range or at lower value than control for all stations. Chromium (Cr) in Meleta (3.08 mg/kg dw) and Bomba (3.80 mg/kg dw) and Cadmium values in all stations (1.21–2.41 mg/kg dw) were above control. Meleta, stations from the gulf of Syrt and the three eastern stations were the most affected stations by nickel (max at 5.83 mg/kg dw in Syrt) when zinc was in the same range (141–197 mg/kg dw) and above the control (92 mg/kg dw) at all stations. Polycyclic aromatic hydrocarbon (PAH) levels were found in the range of 16.8–42.8 mg/kg (dry weight) indicating low levels along the Libyan coast with acenaphthene and benzo (a, b, k) pyrenes detected mainly in western Libya. The study of PAH ratios indicated a mixed petrogenic/pyrolytic origin. The only polychlorinated biphenyls (PCBs) found in Libya were PCB 101 in one location and PCB 153 in Tripoli, Garrapoli, Syrt, Ras Lanuf and Benghazi (1.2–1.9 μg/kg dw). Insecticides were lower than control in all stations except DDT, only detected in Misratah (3.5 μg/kg dw). Overall, the results indicated a low background contamination and a low pollution extent according to the environmental pressure occurring offshore the Libyan coast.     

Behaviour of oxyfluorfen in soils amended with edaphic biostimulants/biofertilizers obtained from sewage sludge and chicken feathers. Effects on soil biological properties

We studied the behaviour of oxyfluorfen herbicide at a rate of 4 l ha^?1 on biological properties of a Calcaric Regosol amended with two edaphic biostimulants/biofertilizers (SS, derived from sewage sludge; and CF, derived from chicken feathers). Oxyfluorfen was surface broadcast on 11 March 2013. Two days after application of oxyfluorfen to soil, both biostimulants/biofertilizers (BS) were also applied to the soil. An unamended soil without oxyfluorfen was used as control. For 2, 4, 7, 9, 20, 30, 60, 90 and 120 days of the application of herbicide to the soil and for each treatment, the soil dehydrogenase, urease, β-glucosidase and phosphatase activities were measured. For 2, 7, 30 and 120 days of the application of herbicide to the soil and for each treatment, soil microbial community was determined. The application of both BS to soil without the herbicide increased the enzymatic activities and soil biodiversity, mainly at 7 days of beginning the experiment. However, this stimulation was higher in the soil amended with SS than for CF. The application of herbicide in organic-amended soils decreased the inhibition of soil enzymatic activities and soil biodiversity. Possibly, the low-molecular-weight protein content easily assimilated by soil microorganisms is responsible for less inhibition of these soil biological properties.     

Biochemical and standard toxic effects of acetaminophen on the macrophyte species Lemna minor and Lemna gibba

Acetaminophen is globally one of the most prescribed drugs due to its antipyretic and analgesic properties. However, it is highly toxic when the dosage surpasses the detoxification capability of an exposed organism, with involvement of an already described oxidative stress pathway. To address the issue of the ecotoxicity of acetaminophen, we performed acute exposures of two aquatic plant species, Lemna gibba and Lemna minor, to this compound. The selected biomarkers were number of fronds, biomass, chlorophyll content, lipid peroxidation (TBARS assay), and proline content. Our results showed marked differences between the two species. Acetaminophen caused a significant decrease in the number of fronds (EC₅₀?=?446.6 mg/L), and the establishment of a dose-dependent peroxidative damage in L. minor, but not in L. gibba. No effects were reported in both species for the indicative parameters chlorophyll content and total biomass. However, the proline content in L. gibba was substantially reduced. The overall conclusions point to the occurrence of an oxidative stress scenario more prominent for L. minor. However, the mechanisms that allowed L. gibba to cope with acetaminophen exposure were distinct from those reported for L. minor, with the likely involvement of proline as antioxidant.     

Effects of anticholinesterase drugs on biomarkers and behavior of pumpkinseed, Lepomis gibbosus (Linnaeus, 1758)

The presence of pharmaceutical residues in the aquatic environment has recently received great attention, as potential adverse effects may arise from their presence. Inhibition of cholinesterases (ChE) has been widely used as an environmental biomarker of exposure to organophosphates (OP) and carbamate (CB) pesticides. However, other widespread anthropogenic contaminants - including pharmaceutical drugs - can exert toxic effects through ChE inhibition. Studies with aquatic species have shown that inhibition of ChE is associated with behavioral changes. Bearing this in mind, this work aimed to study the effects on individual behavior and acetylcholinesterase (AChE) activity of selected tissues of Lepomis gibbosus, after exposure to the anticholinesterasic drugs neostigmine and pyridostigmine. Results revealed that neostigmine significantly decreased the activity of AChE in the head (LOEC = 100 mg L(-1)), but not in dorsal muscle. On the other hand, pyridostigmine significantly decreased the activity of AChE in both the head (LOEC = 0.001 mg L(-1)) and dorsal muscle homogenates (LOEC = 100 mg L(-1)). The impairment of this enzymatic form was attained at ecologically relevant concentrations (in the case of pyridostigmine, for head AChE), which is an interesting finding, specially considering that these toxic effects occurred for a pharmaceutical compound. Contrarily, there were no significant differences in the behavior of L. gibbosus in any parameter, for neither drug. These results suggest that the behavioral parameters analyzed (scototaxis and lethargy) in L. gibbosus could not be regarded as suitable markers to assess the effects of drugs such as neostigmine and pyridostigmine. In contrast, the pattern of response elicited by cholinesterasic inhibition showed the usefulness of this toxicological parameter for the assessment of pharmaceuticals in the environment, namely anticholinesterasics.     

Mobility of selected trace elements in Mediterranean red soil amended with phosphogypsum: experimental study

Soil amendment by phosphogypsum (PG) application becomes of increasing importance in agriculture. This may lead, however, to soil, plant, and groundwater contamination with trace elements (TEs) inherently present in PG. Monitoring of selected TEs (Pb, Zn, Cu, and Cd) distribution and mobility in a Mediterranean red soil profile has been performed in soil parcels applied with PG over a 16-month period. Concentrations were measured in soil and plant samples collected from various depth intervals at different points in time. TEs sequential extraction was performed on soil and PG samples. Results showed soil profile enrichment peaked 5 months after PG application for Cd, and 12 months for Pb, Zn, and Cu. Rainwater, pH, total organic carbon, and cationic exchange capacity were the main controlling factors in TEs accumulation in soils. Cd was transferred to a soil depth of about 20 cm. Zn exhibited mobility towards deeper layers. Pb and Cu were accumulated in around 20-55-cm-deep layers. PG increased the solubility of the studied TEs; PG-applied soils contained TEs bound to exchangeable and acid-soluble fractions in higher percentages than reference soil. Pb, Zn, and Cu were sorbed into mineral soil phases, while Cd was mainly found in the exchangeable (bio-available) form. The order of TEs decreasing mobility was Zn > Cd > Pb > Cu. Roots and leaves of existed plants, Cichorium intybus L., accumulated high concentrations of Cd (1-2.4 mg/kg), exceeding recommended tolerable levels, and thus signifying potential health threats through contaminated crops. It was therefore recommended that PG should be applied in carefully established, monitored, and controlled quantities to agricultural soils.