Biomonitoring acidic drainage impact in a complex setting using periphyton

Acid mine drainage (AMD) often exerts various environmental pressures on nearby water courses: chemical stress from low pH and dissolved metals; physical stress from metal oxide deposits. Affected streams can thus display a spatially variable combination of stress agents that may complicate its biomonitoring using native communities such as periphyton. Here, we have measured water and periphyton variables in four streams that surround an abandoned copper mine to determine which periphyton attributes consistently detected AMD impact in a complex environmental setting. Seventeen years after the end of commercial exploitation, the abandoned mine still decreases water quality in nearby streams: moderate acidification, very high metal load (Al, Ni, Cu, Zn), and a conspicuous presence of metal oxide deposits with diverse composition. Even under the resultant complex pattern of polluted conditions, periphyton was a reliable bioindicator of AMD. Epilithic diatom taxa tolerant of acidic conditions increased in AMD sites and, at severely impacted locations, species richness decreased. Also, algal biomass may have been negatively affected in some stream reaches affected by metal oxide deposits. Other periphyton attributes (total biomass, diatom diversity) seemed mostly unrelated to AMD. Diatom assemblage composition was the most sensitive and consistent bioindicator of mine drainage; besides, it rendered a biological assessment of AMD impact that largely coincided with the physicochemical evaluation. Still, including other taxonomic (proportion of acid-tolerant diatom species, diatom richness) and non-taxonomic (algal biomass) attributes in the biomonitoring procedure rendered a more comprehensive assessment of the negative consequences generated by AMD.     

Dependence of Ozone Biomonitoring on Meteorological Conditions of Different Sites in Catalonia (N.E. Spain)

Evaluation of visual symptoms of ozone damage was conducted in the network of bioindicator rural stations of Catalonia (NE Spain) every 14 days from May to October. Damage rates of ozone (and consequently, ozone biomonitoring capacity of bioindicators) were found to vary highly in time and space depending on the local environmental and meteorological conditions. Lower ozone damage to foliage was produced when meteorological conditions favour stomata resistance. Modulatory effects of meteorological conditions need to be considered in biomonitoring and when modeling plant ozone doses and damage.     

Assessment of phenylurea herbicides sorption on various Mediterranean soils affected by irrigation with wastewater

The retention values of two herbicides, chlorotoluron and isoproturon, in five Mediterranean soils were assessed by two different approaches, a dynamic method, using a batch technique (BT) and a static method, using a soil saturated paste (SP). The SP method led in all cases to lower herbicide sorption when compared with BT, although pesticide distribution constants from both methods were linearly related for the set of used soils (R² ? 0.99) showing that both methods similarly reflected the behaviour of the different soils. Low-quality water, evaluated by employing recycled urban wastewater, did not modify herbicide sorption when compared with high quality water, in any soil and with any method.     

Occurrence of cyclophosphamide and epirubicin in wastewaters by direct injection analysis–liquid chromatography–high-resolution mass spectrometry

Background, aim, and scope

According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography?Chigh-resolution mass spectrometry (LC?COrbitrap?CMS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents.

Materials and methods

Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200?mg hydrophilic?Clipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP.

Results and discussion

Cyclophosphamide and epirubicin were recovered after 50?mL preconcentration on solid-phase extraction 200?mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500?mL of water. Limits of detection were of 0.35 and 2.77?ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1???g/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85?ng?L^?1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8???g?L^?1.

Conclusions

The results obtained in this study demonstrate the capability of LC?COrbitrap?CMS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.     

Cr(VI) and COD removal from landfill leachate by polyculture constructed wetland at a pilot scale

Four subsurface horizontal-flow constructed wetlands (CWs) at a pilot scale planted with a polyculture of the tropical plants Gynerium sagittatum (Gs), Colocasia esculenta (Ce) and Heliconia psittacorum (He) were evaluated for 7 months. The CW cells with an area of 17.94 m² and 0.60 m (h) each and 0.5 m of gravel were operated at continuous gravity flow (Q?=?0.5 m³ day^?1) and a theoretical HRT of 7 days each and treating landfill leachate for the removal of filtered chemical oxygen demand (COD_f), BOD₅, TKN, NH₄ ⁺, NO₃ ^?, PO₄ ^3?–P and Cr(VI). Three CWs were divided into three sections, and each section (5.98 m²) was seeded with 36 cuttings of each species (plant density of six cuttings per square metre). The other unit was planted randomly. The final distributions of plants in the bioreactors were as follows: CW I (He-Ce-Gs), CW II (randomly), CW III (Ce-Gs-He) and CW IV (Gs-He-Ce). The units received effluent from a high-rate anaerobic pond (BLAAT®). The results show a slightly alkaline and anoxic environment in the solid-liquid matrix (pH?=?8.0; 0.5–2 mg L^?1 dissolved oxygen (DO)). COD_f removal was 67 %, BOD₅ 80 %, and TKN and NH₄ ⁺ 50–57 %; NO₃ ^? effluents were slightly higher than the influent, PO₄ ^3?–P (38 %) and Cr(VI) between 50 and 58 %. CW IV gave the best performance, indicating that plant distribution may affect the removal capacity of the bioreactors. He and Gs were the plants exhibiting a translocation factor (TF) of Cr(VI) >1. The evaluated plants demonstrated their suitability for phytoremediation of landfill leachate, and all of them can be categorized as Cr(VI) accumulators. The CWs also showed that they could be a low-cost operation as a secondary system for treatment of intermediated landfill leachate (LL).     

Amendment application in a multi-contaminated mine soil: effects on soil enzymatic activities and ecotoxicological characteristics

Several amendments were tested on soils obtained from an arsenopyrite mine, further planted with Arrhenatherum elatius and Festuca curvifolia, in order to assess their ability to improve soil's ecotoxicological characteristics. The properties used to assess the effects were: soil enzymatic activities (dehydrogenase, β-glucosidase, acid phosphatase, urease, protease and cellulase), terrestrial bioassays (Eisenia fetida mortality and avoidance behaviour), and aquatic bioassays using a soil leachate (Daphnia magna immobilisation and Vibrio fischeri bioluminescence inhibition). The treatment with FeSO₄ 1 % w/w was able to reduce extractable As in soil, but increased the extractable Cu, Mn and Zn concentrations, as a consequence of the decrease in soil pH, in relation to the unamended soil, from 5.0 to 3.4, respectively. As a consequence, this treatment had a detrimental effect in some of the soil enzymatic activities (e.g. dehydrogenase, acid phosphatase, urease and cellulase), did not allow plant growth, induced E. fetida mortality in the highest concentration tested (100 % w/w), and its soil leachate was very toxic towards D. magna and V. fischeri. The combined application of FeSO₄ 1 % w/w with other treatments (e.g. CaCO₃ 1 % w/w and paper mill 1 % w/w) allowed a decrease in extractable As and metals, and a soil pH value closer to neutrality. As a consequence, dehydrogenase activity, plant growth and some of the bioassays identified those as better soil treatments to this type of multi-contaminated soil.     

Competitive removal of pharmaceuticals from environmental waters by adsorption and photocatalytic degradation

This work explores the competitive removal of pharmaceuticals from synthetic and environmental waters by combined adsorption-photolysis treatment. Five drugs usually present in waterways have been used as target compounds, some are pseudo-persistent pollutants (carbamazepine, clofibric acid, and sulfamethoxazole) and others are largely consumed (diclofenac and ibuprofen). The effect of the light source on adsorption of drugs onto activated carbons followed by photolysis with TiO₂ was assessed, being UV-C light the most effective for drug removal in both deionized water and river water. Different composites prepared from titania nanoparticles and powdered activated carbons were tested in several combined adsorption-photocatalysis assays. The composites prepared by calcination at 400 °C exhibited much better performance than those synthesized at 500 °C, being the C400 composite the most effective one. Furthermore, some synthetic waters containing dissolved species and environmental waters were used to investigate the effect of the aqueous matrix on each drug removal. In general, photocatalyst deactivation was found in synthetic and environmental waters. This was particularly evident in the experiments performed with bicarbonate ions as well as with wastewater effluent. In contrast, tests conducted in seawater showed adsorption and photocatalytic degradation yields comparable to those obtained in deionized water. Considering the peculiarities of substrate competition in each aqueous matrix, the combined adsorption-photolysis treatment generally increased the overall elimination of drugs in water.     

Designing conservation-development policies for the forest frontier

The conservation of forests in expanding frontier landscapes is critically important to maintain intact forest ecosystems and support forest dependent communities. To conserve frontier forests, policy approaches are needed that conserve forests and advance the well-being of local resource dependent communities. To identify such approaches, the forest conservation and development framework (FCDF) was designed to find place-based conservation-development policies that target system leverage-points influencing land-use practices. To demonstrate the utility of the FCDF, a portfolio of conservation-development policies were identified for Peru’s Manu-Tambopata Corridor (MAT) and evaluated by local land-users. Results of the MAT case study show high levels of interest in the proposed policies, but a wide variation in interest levels relative to personal circumstances and policies proposed. Barriers to implementing conservation-development policies in frontier environments were also identified, including high value land-use alternatives generating high opportunity costs for accepting PES payments (e.g., REDD+), insecure land tenure and conflicting authorizations limiting land-users policy choices, and broad demographic diversity among local land-users. Collectively, this research suggests the FCDF is a useful approach for identifying policies matched to local conditions that advance conservation and human development. This research also indicates policy design in frontier environments is most effective when adapted to local conditions, seeks to identify a mix of complementary policies, and is targeted at key system variables influencing land-use practices (i.e., system leverage-points). Importantly, the MAT case study also highlights how even in rapidly changing frontier landscapes, land-users are interested in policies that advance conservation and development goals.     

Arsenic, chromium and mercury removal using mussel shell ash or a sludge/ashes waste mixture

Different batches of valued mussel shell and waste mussel shell ash are characterised. Shell ash has pH?>?12 and high electrical conductivities (between 16.01 and 27.27 dS?m^?1), while calcined shell shows pH values up to 10.7 and electrical conductivities between 1.19 and 3.55 dS?m^?1. X-ray fluorescence, nitric acid digestion and water extractions show higher concentrations in shell ash for most parameters. Calcite is the dominant crystalline compound in this ash (95.6 %), followed by aragonite. Adsorption/desorption trials were performed for mussel shell ash and for a waste mixture including shell ash, sewage sludge and wood ash, showing the following percentage adsorptions: Hg(II) >94 %, As(V) >96 % and Cr(VI) between 11 and 30 % for shell ash; Hg(II) >98 %, As(V) >88 % and Cr(VI) between 30 and 88 % for the waste mixture. Hg and As desorption was <5 % for both shell ash and the waste mixture, while Cr desorption was between 92 and 45 % for shell ash, and between 19 and 0 % for the mixture. In view of that, mussel shell ash and the mixture including shell ash, sewage sludge and wood ash could be useful for Hg(II) and As(V) removal.     

Comparing the response of biochemical indicators (biomarkers) and biological indices to diagnose the ecological impact of an oil spillage in a Mediterranean river (NE Catalunya, Spain)

Three biomarkers of hydrocarbon exposure, liver 7-ethoxyresourfin-O-deethylase activity (EROD), fluorescent hydrocarbon compounds (FACs) in bilis, and the liver antioxidant enzyme catalase (CAT) were examined in the autochthonous fish species Barbus meridionalis collected in the river Fluvià (NE Catalunya, Spain) after an oil spillage. Four different locations were sampled, including the impacted site, upstream and downstream sites and a reference site. Biomarker responses were compared with diatom and macroinvertebrate community assemblage metrics (Specific Pollution Sensitivity index - IPS, and Iberian Biological Monitoring Working Party - IBMWP, respectively). Chemical analyses denoted that polycyclic aromatic hydrocarbon levels in sediment were much higher at the impacted site than in downstream reaches. Four fold increase of EROD activity together with increased levels of biliary FACs in barbs collected at the spilled site indicated exposure of inhabiting fish to the oil. Additionally, CAT activity was significantly depressed (four fold) when compared to other stations, thus suggesting that fish collected from the impacted sites could be more susceptible to suffer oxidative stress. Biological indices (particularly that of the diatom community IPS) showed slight significant effects between control and impacted sites, indicating that more tolerant taxa were favoured because of the oil spillage. These results support the need to include biochemical responses measured in local species in monitoring programmes aimed to diagnose specific pollution effects in stressed river ecosystems.