Effects of particle size on chemical speciation and bioavailability of copper to earthworms (Eisenia fetida) exposed to copper nanoparticles

To investigate the role of particle size on the oxidation, bioavailability, and adverse effects of manufactured Cu nanoparticles (NPs) in soils, we exposed the earthworm Eisenia ferida to a series of concentrations of commercially produced NPs labeled as 20- to 40-nm or < 100-nm Cu in artificial soil media. Effects on growth, mortality, reproduction, and expression of a variety of genes associated with metal homeostasis, general stress, and oxidative stress were measured. We also used X-ray absorption spectroscopy and scanning X-ray fluorescence microscopy to characterize changes in chemical speciation and spatial distribution of the NPs in soil media and earthworm tissues. Exposure concentrations of Cu NPs up to 65 mg kg(-1) caused no adverse effects on ecologically relevant endpoints. Increases in metallothionein expression occurred at concentrations exceeding 20 mg kg(-1) of Cu NPs and concentrations exceeding 10 mg kg(-1) of CuSO4. Based on the relationship of Cu tissue concentration to metallothionein expression level and the spatial distribution and chemical speciation of Cu in the tissues, we conclude that Cu ions and oxidized Cu NPs were taken up by the earthworms. This study suggests that oxidized Cu NPs may enter food chains from soil but that adverse effects in earthworms are likely to occur only at relatively high concentrations (> 65 mg Cu kg(-1) soil).     

Quantifying nitrogen process rates in a constructed wetland using natural abundance stable isotope signatures and stable isotope amendment experiments

This study describes the spatial variability in nitrogen (N) transformation within a constructed wetland (CW) treating domestic effluent. Nitrogen cycling within the CW was driven by settlement and mineralization of particulate organic nitrogen and uptake of NO3-. The concentration of NO3- was found to decrease, as the delta15N-NO3- signature increased, as water flowed through the CW, allowing denitrification rates to be estimated on the basis of the degree of fractionation of delta15N-NO3-. Estimates of denitrification hinged on the determination of a net isotope effect (eta), which was influenced byprocesses that enrich or deplete 15NO3- (e.g., nitrification), as well as the rate constants associated with the different processes involved in denitrification (i.e., diffusion and enzyme activity). The influence of nitrification on eta was quantified; however, it remained unclear how eta varied due to variability in denitrification rate constants. A series of stable isotope amendment experiments was used to further constrain the value of eta and calculate rates of denitrification, and nitrification, within the wetland. The maximum calculated rate of denitrification was 956 +/- 187 micromol N m(-2) h(-1), and the maximum rate of nitrification was 182 +/- 28.9 micromol N m(-2) h(-1). Uptake of NO3- was quantitatively more important than denitrification throughoutthe wetland. Rates of N cycling varied spatially within thewetland, with denitrification dominating in the downstream deoxygenated region of the wetland. Studies that use fractionation of N to derive rate estimates must exercise caution when interpreting the net isotope effect. We suggest a sampling procedure for future natural abundance studies that may help improve the accuracy of N cycling rate estimates.     

Decontamination of water polluted by heavy metals with Taro (Colocasia esculenta) cultured in a hydroponic NFT system

The toxicity and bioaccumulation of two heavy metals—lead (Pb) and cadmium (Cd)—in a semi-aquatic plant, Colocasia esculenta (L. Schott), from a synthetic heavy metal solution were studied. Young plants of equal size were grown hydroponically in shallow raceways containing Hoagland medium amended with 20, 40, and 60 mg l^?1 of Pb and 2, 4, and 6 mg l^?1 of Cd. The medium containing heavy metals was allowed to flow through the raceways with a change in influent heavy metal solution on every 5th day. The experiment was continued for 20 days. A set of control raceways—one comprised of nutrient medium with heavy metal supplements, devoid of plants, and another with the plants and nutrient medium having no metal supplement—was also simultaneously run. Chlorosis in the leaves was the prominent toxicity symptom observed due to Pb and Cd on the test plants. A significant decrease in the relative growth, biomass productivity, and total chlorophyll content were noticed in the plants with an increase in concentration of metal supplement in the solution and exposure time. Both metals accumulated to higher concentrations in the roots than in shoots, suggesting that the metals were bound to the root cells and their translocation to the leaves was limited. The results of the 20-day-long experiments indicate that from a phytoremediation perspective, C. esculenta is a promising plant species for remediation of wastewater polluted with lower concentrations of Pb and Cd.     

Indication of airborne pollution by birch and spruce in the vicinity of copper smelter

The aim of the study was determination of air pollution impact of the copper smelter in Bor and its surroundings (Serbia) by assessing the suitability of birch (Betula pendula Roth.) and spruce (Picea abies L.) for the purposes of biomonitoring and comparing it with previously published data from the same study area. The concentrations of Cu, Zn, Pb and Mn in leaves/needles, branches, roots and soil were determined. Sampling was performed during 2009 in two zones with high load of air pollution due to copper mining and smelting activities, and one background zone. Metal accumulation and translocation was evaluated in terms of biological factors. In addition, plant enrichment factor was calculated. According to the results, plant foliage was not enriched through soil, which indicates absorption from the air, with both species acting as excluders of Cu, Pb, Zn and Mn. Leaves were more enriched with all the metals than needles, indicating a better response of birch to airborne pollution than spruce. Cluster analysis showed different level of pollution at the sites, while correlations between Cu and Pb obtained by Principal Component Analysis indicated their anthropogenic origin. Regarding previously published results, beside birch leaves, pine needles (which showed higher level of response to pollution compared to linden leaves) could be applied in air biomonitoring surveys near copper smelters.     

Micropollutants in urban stormwater: occurrence,concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments

This study aimed at: (a) providing information on the occurrence and concentration ranges in urban stormwater for a wide array of pollutants (n?=?77); (b) assessing whether despite the differences between various catchments (land use, climatic conditions, etc.), the trends in terms of contamination level are similar; and (c) analyzing the contribution of total atmospheric fallout (TAF) with respect to sources endogenous to this contamination. The studied contaminants include conventional stormwater contaminants (polycyclic aromatic hydrocarbons (PAHs), Zn, Cu, Pb, etc.), in addition to poorly or undocumented pollutants such as nonylphenol and octylphenol ethoxylates (NPnEO and OPnEO), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs), a wide variety of pesticides, and various metals of relevance (As, Ti, Sr, V). Sampling and analysis were performed using homogeneous methods on three urban catchments with different land use patterns located in three distinct French towns. For many of these pollutants, the results do not allow highlighting a significant difference in stormwater quality at the scale of the three urban catchments considered. Significant differences were, however, observed for several metals (As, Cr, Cu, Ni, Sr and Zn), PAHs, and PBDEs, though this assessment would need to be confirmed by further experiments. The pollutant distributions between dissolved and particulate phases were found to be similar across the three experimental sites, thus suggesting no site dependence. Lastly, the contributions of TAF to stormwater contamination for micropollutants were quite low. This finding held true not only for PAHs, as previously demonstrated in the literature, but also for a broader range of molecules such as BPA, NPnEO, OPnEO, and PBDEs, whose high local production is correlated with the leaching of urban surfaces, buildings, and vehicles.     

Investigation of pharmaceutical metabolites in environmental waters by LC-MS/MS

Pharmaceuticals, once ingested, are commonly metabolized in the body into more polar and soluble forms. These compounds might not be completely removed in the wastewater treatment plants and consequently being discharged into the aquatic ecosystem. In this work, a multi-class sensitive method for the analysis of 21 compounds, including 7 widely consumed pharmaceuticals and 14 relevant metabolites, has been developed based on the use of UHPLC-MS/MS in selected reaction monitoring (SRM) mode. The method was validated in six surface waters (SW) and six effluent wastewaters (EWW) at realistic concentration levels that can be found in waters. The optimized method was applied to the analysis of different types of water samples (rivers, lakes and effluent wastewater), detecting nearly all the parent compounds and metabolites investigated in this work. This fact illustrates that not only pharmaceuticals but also their metabolites are commonly present in these types of waters. Analytical research and monitoring programs should be directed not only towards parent pharmaceuticals but also towards relevant metabolites to have a realistic overview of the impact of pharmaceuticals in the aquatic environment.     

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments

The study describes the environmental monitoring of anionic surfactants―alcohol sulfates (AS) and alcohol ethoxysulfates (AES)—in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry analysis (LC–MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg^?1 for AS, from 3.04 to 10.68 mg kg^?1 for AES–C₁₂E_x and from 3.83 to 11.56 mg kg^?1 for AES–C₁₄E_x.     

Mass loads of dissolved and particulate mercury and other trace elements in the Mt. Amiata mining district,Southern Tuscany (Italy)

Total dissolved and particulate mercury (Hg), arsenic (As), and antimony (Sb) mass loads were estimated in different seasons (March and September 2011 and March 2012) in the Paglia River basin (PRB) (central Italy). The Paglia River drains the Mt. Amiata Hg district, one of the largest Hg-rich regions worldwide. Quantification of Hg, As, and Sb mass loads in this watershed allowed (1) identification of the contamination sources, (2) evaluation of the effects of Hg on the environment, and (3) determination of processes affecting Hg transport. The dominant source of Hg in the Paglia River is runoff from Hg mines in the Mt. Amiata region. The maximum Hg mass load was found to be related to runoff from the inactive Abbadia San Salvatore Mine (ASSM), and up to 30 g day^?1 of Hg, dominantly in the particulate form, was transported both in high and low flow conditions in 2011. In addition, enrichment factors (EFs) calculated for suspended particulate matter (SPM) were similar in different seasons indicating that water discharge controls the quantities of Hg transported in the PRB, and considerable Hg was transported in all seasons studied. Overall, as much as 11 kg of Hg are discharged annually in the PRB and this Hg is transported downstream to the Tiber River, and eventually to the Mediterranean Sea. Similar to Hg, maximum mass loads for As and Sb were found in March 2011, when as much as 190 g day^?1 each of As and Sb were measured from sites downstream from the ASSM. Therefore, the Paglia River represents a significant source of Hg, Sb, and As to the Mediterranean Sea.     

A hybrid biological process of indoor air treatment for toluene removal

Bioprocesses, such as biofiltration, are commonly used to treat industrial effluents containing volatile organic compounds (VOCs) at low concentrations. Nevertheless, the use of biofiltration for indoor air pollution (IAP) treatment requires adjustments depending on specific indoor environments. Therefore, this study focuses on the convenience of a hybrid biological process for IAP treatment. A biofiltration reactor using a green waste compost was combined with an adsorption column filled with activated carbon (AC). This system treated a toluene-micropolluted effluent (concentration between 17 and 52 µg/m³), exhibiting concentration peaks close to 733 µg/m³ for a few hours per day. High removal efficiency was obtained despite changes in toluene inlet load (from 4.2 × 10^?3 to 0.20 g/m³/hr), which proves the hybrid system’s effectiveness. In fact, during unexpected concentration changes, the efficiency of the biofilter is greatly decreased, but the adsorption column maintains the high efficiency of the entire process (removal efficiency [RE] close to 100%). Moreover, the adsorption column after biofiltration is able to deal with the problem of the emission of particles and/or microorganisms from the biofilter.

ImplicationsIndoor air pollution is nowadays recognized as a major environmental and health issue. This original study investigates the performance of a hybrid biological process combining a biofilter and an adsorption column for removal of indoor VOCs, specifically toluene.