Showing papers in "Environmental Science: Processes & Impacts in 2013"

Identification of polymer types and additives in marine microplastic particles using pyrolysis-GC/MS and scanning electron microscopy

Abstract: Any assessment of plastic contamination in the marine environment requires knowledge of the polymer type and the additive content of microplastics. Sequential pyrolysis-gas chromatography coupled to mass spectrometry (Pyr-GC/MS) was applied to simultaneously identify polymer types of microplastic particles and associated organic plastic additives (OPAs). In addition, a scanning electron microscope equipped with an energy-dispersive X-ray microanalyser was used to identify the inorganic plastic additives (IPAs) contained in these particles. A total of ten particles, which were optically identified as potentially being plastics, were extracted from two sediment samples collected from Norderney, a North Sea island, by density separation in sodium chloride. The weights of these blue, white and transparent fragments varied between 10 and 350 μg. Polymer types were identified by comparing the resulting pyrograms with those obtained from the pyrolysis of selected standard polymers. The particles consisted of polyethylene (PE), polypropylene, polystyrene, polyamide, chlorinated PE and chlorosulfonated PE. The polymers contained diethylhexyl phthalate, dibutyl phthalate, diethyl phthalate, diisobutyl phthalate, dimethyl phthalate, benzaldehyde and 2,4-di-tert-butylphenol. Sequential Py-GC/MS was found to be an appropriate tool for identifying marine microplastics for polymer types and OPAs. The IPAs identified were titanium dioxide nanoparticles (TiO2-NPs), barium, sulphur and zinc. When polymer–TiO2 composites are degraded in the marine environment, TiO2-NPs are probably released. Thus, marine microplastics may act as a TiO2-NP source, which has not yet been considered.

Silver nanoparticles in the environment

Abstract: Silver nanoparticles (AgNPs) are well known for their excellent antibacterial ability and superior physical properties, and are widely used in a growing number of applications ranging from home disinfectants and medical devices to water purificants. However, with the accelerating production and introduction of AgNPs into commercial products, there is likelihood of release into the environment, which raises health and environmental concerns. This article provides a critical review of the state-of-knowledge about AgNPs, involving the history, analysis, source, fate and transport, and potential risks of AgNPs. Although great efforts have been made in each of these aspects, there are still many questions to be answered to reach a comprehensive understanding of the positive and negative effects of AgNPs. In order to fully investigate the fate and transport of AgNPs in the environment, appropriate methods for the preconcentration, separation and speciation of AgNPs should be developed, and analytical tools for the characterization and detection of AgNPs in complicated environmental samples are also urgently needed. To elucidate the environmental transformation of AgNPs, the behavior of AgNPs should be thoroughly monitored in complex environmental relevant conditions. Furthermore, additional in vivo toxicity studies should be carried out to understand the exact toxicity mechanism of AgNPs, and to predict the health effects to humans.

Iron nanoparticles for environmental clean-up: recent developments and future outlook.

Abstract: Nanoscale zero-valent iron (nZVI) is one of the most extensively applied nanomaterials for groundwater and hazardous waste treatment. In the past fifteen years, progress made in several key areas has deepened our understanding of the merits and uncertainties of nZVI-based remediation applications. These areas include the materials chemistry of nZVI in its simple and modified forms, the nZVI reactivity with a wide spectrum of contaminants in addition to the well-documented chlorinated solvents, methods to enhance the colloidal stability and transport properties of nZVI in porous media, and the effects of nZVI amendment on the biogeochemical environment. This review aims to provide an up-to-date account of advancement in these areas as well as insights gained through field experience.

Human exposure to aluminium

Abstract: Human activities have circumvented the efficient geochemical cycling of aluminium within the lithosphere and therewith opened a door, which was previously only ajar, onto the biotic cycle to instigate and promote the accumulation of aluminium in biota and especially humans. Neither these relatively recent activities nor the entry of aluminium into the living cycle are showing any signs of abating and it is thus now imperative that we understand as fully as possible how humans are exposed to aluminium and the future consequences of a burgeoning exposure and body burden. The aluminium age is upon us and there is now an urgent need to understand how to live safely and effectively with aluminium.

Impact of metallic and metal oxide nanoparticles on wastewater treatment and anaerobic digestion

Abstract: Metallic and metal oxide nanomaterials have been increasingly used in consumer products (e.g. sunscreen, socks), the medical and electronic industries, and environmental remediation. Many of them ultimately enter wastewater treatment plants (WWTPs) or landfills. This review paper discusses the fate and potential effects of four types of nanoparticles, namely, silver nanoparticles (AgNPs), nano ZnO, nano TiO2, and nano zero valent iron (NZVI), on waste/wastewater treatment and anaerobic digestion. The stabilities and chemical properties of these nanoparticles (NPs) result in significant differences in antimicrobial activities. Analysis of published data of metallic and metal oxide NPs suggests that oxygen is often a prerequisite for the generation of reactive oxygen species (ROS) for AgNPs and NZVI, while illumination is necessary for ROS generation for nano TiO2 and nano ZnO. Furthermore, such nanoparticles are capable of being oxidized or dissolved in water and can release metal ions, leading to metal toxicity. Therefore, AgNPs and nano TiO2 are chemically stable NPs that have no adverse effects on microbes under anaerobic conditions. Although the toxicity of nanomaterials has been studied intensively under aerobic conditions, more research is needed to address their fate in anaerobic waste/wastewater treatment systems and their long-term effects on the environment.

A review on cylindrospermopsin: the global occurrence, detection, toxicity and degradation of a potent cyanotoxin

Abstract: Cylindrospermopsin is an important cyanobacterial toxin found in water bodies worldwide. The ever-increasing and global occurrence of massive and prolonged blooms of cylindrospermopsin-producing cyanobacteria poses a potential threat to both human and ecosystem health. Its toxicity is associated with metabolic activation and may involve mechanisms that adversely affect a wide variety of targets in an organism. Cylindrospermopsin has been shown to be cytotoxic, dermatotoxic, genotoxic, hepatotoxic in vivo, developmentally toxic, and may be carcinogenic. Human exposure may occur through drinking water, during recreational activities and by consuming foods in which the toxin may have bioaccumulated. Drinking water shortages of sufficient quality coupled with growing human pressures and climate variability and change necessitate an integrated and sustainable water management program. This review presents an overview of the importance of cylindrospermopsin, its detection, toxicity, worldwide distribution, and lastly, its chemical and biological degradation and removal by natural processes and drinking water treatment processes.

Biological accumulation of engineered nanomaterials: a review of current knowledge

Abstract: Due to the widespread use of engineered nanomaterials (ENMs) in consumer and industrial products, concerns have been raised over their impacts once released into the ecosystems. While there has been a wealth of studies on the short-term acute toxic effects of ENMs over the past decade, work on the chronic endpoints, such as biological accumulation, has just begun to increase in last 2–3 years. Here, we comprehensively review over 65 papers on the biological accumulation of ENMs under a range of ecologically relevant exposure conditions in water, soil or sediment with the focus on quantitative comparison among these existing studies. We found that daphnid, fish, and earthworm are the most commonly studied ecological receptors. Current evidence suggests that ENM accumulation level is generally low in fish and earthworms with logarithmic bioconcentration concentration factor and biota-sediment accumulation factor ranging from 0.85–3.43 (L kg−1) and −2.21–0.4 (kg kg−1), respectively. ENMs accumulated in organisms at the lower trophic level can transfer to higher trophic level animals with the occurrence of biomagnification varying depending on the specific food chain studied. We conclude the review by identifying the challenges and knowledge gaps and propose paths forward.

How physico-chemical characteristics of nanoparticles cause their toxicity: complex and unresolved interrelations

Abstract: The increased use of and interest in nanoparticles (NPs) have resulted in an enormous amount of NPs with different compositions and physico-chemical properties. These unique properties not only determine their utility for (bio-medical) applications, but also their toxicity. Recently, “nano-researchers” became aware of the importance of determining the characteristics since they might be predictors of their toxicity. Currently, we face a large set of (non-coordinated) experiments with miscellaneous objectives resulting in a large quantity of available (and often incomplete) data, which hamper the unraveling of the complex interrelated NP characteristics with experimental results. Here, we try to link different critical physico-chemical characteristics separately with toxicity observed in both in vitro and in vivo models.

Release of TiO2 from paints containing pigment-TiO2 or nano-TiO2 by weathering

Abstract: The release of nanomaterials from products and applications that are used by industry and consumers has only been studied to a very limited extent. The amount and the characteristics of the released particles determine the potential environmental exposure. In this work we investigated the release of Ti from paints containing pigment-TiO2 and nano-TiO2. Panels covered with paint with and without nano-TiO2 were exposed to simulated weathering by sunlight and rain in climate chambers. The same paints were also studied in small-scale leaching tests to elucidate the influence of various parameters on the release such as composition of water, type of support and UV-light. Under all conditions we only observed a very low release close to background values, less than 1.5 μg l−1 in the climate chamber over 113 irrigations per drying cycle and between 0.5 and 14 μg l−1 in the leaching tests, with the highest concentrations observed after prolonged UV-exposure. The actual release of Ti over the 113 weathering cycles was only 0.007% of the total Ti, indicating that TiO2 was strongly bound in the paint. Extraction of UV-exposed and then milled paint resulted in about 100-times larger release of Ti from the nano-TiO2 containing paint whereas the paint with only pigment-TiO2 did not show this increase. This indicated that the release of Ti from the paints is an effect of the addition of nano-TiO2, either by photocatalytic degradation of the organic paint matrix (observed by electron microscopic imaging of the paint surface) or by direct release of nano-TiO2. Our work suggests that paints containing nano-TiO2 may release only very limited amounts of materials into the environment, at least over the time-scales investigated in this work.

Comparative evaluation of impact of Zn and ZnO nanoparticles on brine shrimp (Artemia salina) larvae: effects of particle size and solubility on toxicity

Abstract: Brine shrimp (Artemia salina) larvae were exposed to different sizes of zinc (Zn) and zinc oxide (ZnO) nanoparticles (NPs) to evaluate their toxicity in marine aquatic ecosystems. Acute exposure was conducted in seawater with 10, 50 and 100 mg L−1 concentrations of the NPs for 24 h and 96 h. Phase contrast microscope images confirmed the accumulation of the NPs inside the guts. Artemia were unable to eliminate the ingested particles, which was thought to be due to the formation of massive particles in the guts. Although the suspensions of the NPs did not exhibit any significant acute toxicity within 24 h, mortalities increased remarkably in 96 h and escalated with increasing concentration of NP suspension to 42% for Zn NPs (40–60 nm) (LC50 ∼ 100 mg L−1) and to about 34% for ZnO NPs (10–30 nm) (LC50 > 100 mg L−1). The suspensions of Zn NPs were more toxic to Artemia than those of ZnO NPs under comparable regimes. This effect was attributed to higher Zn2+ levels (ca. up to 8.9 mg L−1) released to the medium from Zn NPs in comparison to that measured in the suspensions of ZnO NPs (ca. 5.5 mg L−1). In addition, the size of the nanopowders appeared to contribute to the observed toxicities. Although the suspensions possessed aggregates of comparable sizes, smaller Zn NPs (40–60 nm) were relatively more toxic than larger Zn NPs (80–100 nm). Likewise, the suspensions of 10–30 nm ZnO NPs caused higher toxicity than those of 200 nm ZnO NPs. Lipid peroxidation levels were substantially higher in 96 h (p < 0.05), indicating that the toxic effects were due to the oxidative stress.

Photosynthetic microbial desalination cells (PMDCs) for clean energy, water and biomass production

Abstract: Current microbial desalination cell (MDC) performances are evaluated with chemical catalysts such as ferricyanide, platinum catalyzed air-cathodes or aerated cathodes. All of these methods improve power generation potential in MDCs, however, they are not preferable for large scale applications due to cost, energy and environmental toxicity issues. In this study, performance of microbial desalination cells with an air cathode and an algae biocathode (Photosynthetic MDC – PMDC) were evaluated, both under passive conditions (no mechanical aeration or mixing). The results indicate that passive algae biocathodes perform better than air cathodes and enhance COD removal and utilize treated wastewater as the growth medium to obtain valuable biomass for high value bioproducts. Maximum power densities of 84 mW m−3 (anode volume) or 151 mW m−3 (biocathode volume) and a desalination rate of 40% were measured with 0.9 : 1 : 0.5 volumetric ratios of anode, desalination and algae biocathode chambers respectively. This first proof-of-concept study proves that the passive mechanisms can be beneficial in enhancing the sustainability of microbial desalination cells.

Antimicrobial nanotechnology: its potential for the effective management of microbial drug resistance and implications for research needs in microbial nanotoxicology

Abstract: The development of antibiotics revolutionized human health, providing a simple cure for once dreaded diseases such as tuberculosis. However, widespread production, use, and mis-use of antibiotics have contributed to the next-generation concern for global public health: the emergence of multiple drug-resistant (MDR) infectious organisms (a.k.a. “superbugs”). Recently, nanotechnology, specifically the use of nanomaterials (NMs) with antimicrobial activity, has been presented as a new defense against MDR infectious organisms. We discuss the potential for NMs to either circumvent microbial resistance or induce its development in light of our current state of knowledge, finding that this question points to a need for fundamental research targeting the molecular mechanisms causing antimicrobial activity in NMs. In the context of current microbial nanotoxicology studies, particularly reductionist laboratory studies, we offer suggestions and considerations for future research, using an illustrative example from our work with silver nanoparticles.

A low-cost particle counter as a realtime fine-particle mass monitor

Abstract: Exposure to particles with aerodynamic diameters less than 2.5 μm is estimated to cause significant morbidity and mortality worldwide leading many countries to develop ambient air pollution standards and guidelines. At local scales, community and environmental justice groups are also concerned about PM2.5 concentrations that may be elevated above regional concentrations typically measured by centrally located monitors and standards as well. In an attempt to develop a low cost, easy to use monitor we evaluated a low-cost optical particle counter, the Dylos™, as a fine particulate mass sensor. Modified into a system called the Berkeley Aerosol Information Recording System (BAIRS), we compared performance against standard commercial instruments in chambers using polystyrene latex spheres, ammonium sulphate, and woodsmoke and in an urban ambient setting. Overall we find that the limit of detection of the BAIRS is less than 1 μg m−3 and the resolution is better than 1 μg m−3 for PM2.5. The BAIRS sizes small (<0.5 μm) particles, and is able to accurately estimate the mass concentration of particles of varying composition including organic, inorganic, and ambient particles. It is able to measure concentrations up to 10.0 mg m−3. In an ambient roof-top test of the BAIRS and a more expensive commercially available light scattering particle monitor the BAIRS response tracked well with the commercial monitor and daily means were within 80% of each other. We conclude that with appropriate modification the system could be developed into an accurate low cost realtime particle mass monitor for use in a wide range of applications.

The biophysicochemical interactions at the interfaces between nanoparticles and aquatic organisms: adsorption and internalization.

Abstract: Nano–bio interfacial interactions that can likely regulate the potential toxicity of nanoparticles (NPs) toward aquatic organisms are receiving increasing research interest worldwide and warrant more investigation. This review presents an overview of already-known nano–bio interactions and some speculations on the interfaces between NPs and aquatic organisms, in order to gain a new insight into the biological effects of NPs in the aquatic environment. The fundamental interfaces between NPs and organism cells and the main biophysicochemical interactions that occur at the nano–bio interfaces are described. The interfacial interactions, focused on adsorption and internalization, during the contact of NPs with microorganisms, hydrophytes, invertebrates and fish were reviewed. The effects of NP properties and suspending states as well as environmental conditions including pH, ionic strength, natural organic matter and other factors on the interfacial interactions were elucidated. Furthermore, the analytical methods employed in the interfacial interaction investigations were also briefly introduced. Future research directions of nano–bio interactions were prospected.

ZnO nanoparticle fate in soil and zinc bioaccumulation in corn plants (Zea mays) influenced by alginate

Abstract: Nanoparticles (NPs) can interact with naturally occurring inorganic and organic substances in soils, which may change their transport behavior in soil and plants. This study was performed in two steps. In the first step, corn (Zea mays) plants were cultivated for one month in soil amended with 10 nm commercial spheroid ZnO NPs at 0–800 mg kg−1 and sodium alginate at 10 mg kg−1. In the second step, the plants were grown with ZnO NPs at 400 mg kg−1 and alginate at 0, 10, 50, and 100 mg kg−1. The dynamics of Zn concentrations in soil solution and Zn accumulation in plant tissues were determined by ICP-OES. Biomass accumulation, chlorophyll concentration, and the activity of antioxidant enzymes in leaves were also quantified. Results indicate that ZnO NPs coexisting with Zn dissolved species were continuously released to the soil solution to replenish the Zn ions or ZnO NPs scavenged by roots. At 400 and 800 mg kg−1, without alginate, ZnO NPs significantly reduced the root and shoot biomass production; however, plants treated with these NP concentrations, plus alginate, had significantly more Zn in tissues with no reduction in biomass production. Alginate significantly reduced the activity of stress enzymes catalase and peroxidase, which could indicate damage in the defense system. The effects of ZnO NPs in a food crop grown in alginate enriched soil, showing an excess of Zn in the aerial parts, are yet to be reported.

The influence of glacial meltwater on alpine aquatic ecosystems: a review

Abstract: The recent and rapid recession of alpine glaciers over the last 150 years has major implications for associated aquatic communities. Glacial meltwater shapes many of the physical features of high altitude lakes and streams, producing turbid environments with distinctive hydrology patterns relative to nival systems. Over the past decade, numerous studies have investigated the chemical and biological effects of glacial meltwater on freshwater ecosystems. Here, we review these studies across both lake and stream ecosystems. Focusing on alpine regions mainly in the Northern Hemisphere, we present examples of how glacial meltwater can affect habitat by altering physical and chemical features of aquatic ecosystems, and review the subsequent effects on the biological structure and function of lakes and streams. Collectively or separately, these factors can drive the overall distribution, diversity and behavior of primary producers, triggering cascading effects throughout the food web. We conclude by proposing areas for future research, particularly in regions where glaciers are soon projected to disappear.

The oxidative toxicity of Ag and ZnO nanoparticles towards the aquatic plant Spirodela punctuta and the role of testing media parameters

Abstract: The toxicity effects of silver (nAg) and zinc oxide (nZnO) engineered nanoparticles (ENPs) on the duckweed Spirodela punctuta were studied to investigate the potential risks posed by these ENPs towards higher aquatic plants. The influence of media abiotic factors on the stability of the ENPs was also evaluated. Marked agglomeration of ENPs was observed after introduction into testing media whereby large particles settled out of suspension and accumulated at the bottom of testing vessels. The high ionic strength (IS) promoted agglomeration of ENPs because it reduced the inter-particle repulsion caused by a reduction in their surface charge. Low dissolution was observed for nAg, reaching only 0.015% at 1000 mg L−1, whilst improved dissolution was observed for nZnO, only falling below analytical quantification at 0.1 mg L−1 and lower. The quantification of free radicals namely, reactive oxygen and nitrogen species (ROS/RNS) and hydrogen peroxide (H2O2), indicated the induction of oxidative stress in plants exposed to the ENPs. A definite dose influence was observed for ROS/RNS volumes in plants exposed to nZnO for 14 days, a response not always observed. The total antioxidant capacity (TAC) and superoxide dismutase (SOD) activity in plants indicated varying degrees of oxidative toxicity caused by exposure to ENPs. This toxicity was driven mainly by particulates in plants exposed to nAg, whilst dissolved Zn2+ was the main driver for toxicity in plants exposed to nZnO. Our findings suggest that the toxicity of nAg and nZnO could be caused by both the particulates and ionic forms, as modified by media properties.

Determination of estrogenic steroids and microbial and photochemical degradation of 17α-ethinylestradiol (EE2) in lake surface water, a case study

Abstract: In this study, a GC-MS technique was applied to determine 17α-ethinylestradiol (EE2), an active ingredient of oral contraceptives, and its fate in Lake Quinsigamond, Massachusetts, USA. To the knowledge of the authors, this is the first study of EE2 and its microbial and photochemical degradation in a lake ecosystem. EE2 was detected at a concentration up to 11.1 ng L−1. At this concentration EE2 may affect the reproduction of fish and other aquatic organisms in the lake due to its high estrogenic activity. EE2 was persistent to the biodegradation by the microorganisms in the lake. Under aerobic conditions a long lag phase (42 days) was observed before the biodegradation of EE2 and a half-life of 108 days was estimated. Under anaerobic conditions, EE2 experienced even a longer acclimation stage (63 days) and a slower microbial degradation in the lake water. The photodegradation of EE2 was rapid in the lake surface water under natural sunlight, with a half-life of less than 2 days in summer sunny days. Compared to biodegradation, photodegradation may represent a predominant removal mechanism for EE2 in natural surface waters.

Modeling the flows of engineered nanomaterials during waste handling.

Abstract: Little is known about the behavior of engineered nanomaterials (ENM) at the interface from the technosphere to the ecosphere. Previous modeling of ENM flows to the environment revealed that significant amounts of ENM enter the waste stream and therefore waste incineration plants and landfills. It is the aim of this study to model the flows of ENM during waste incineration and landfilling in greater depth by including a more detailed description of the different processes and considering ENM-specific transformation reactions. Four substances were modeled: nano-TiO2, nano-ZnO, nano-Ag and carbon nanotube (CNT). These ENM are representative for commonly used materials and products, illustrating a variety of ENM with different behavior. The modeling was performed for Switzerland where almost 100% of the municipal waste and sewage sludge are burned. The mass-based modeling showed that – despite several differences among the models for nano-TiO2, nano-ZnO and nano-Ag (e.g. partial dissolution of nano-ZnO in acid washing of exhaust air or fly ash) – the major ENM flows go from the waste incineration plant to the landfill as bottom ash. All other flows within the system boundary (e.g. with the fly ash) were predicted to be about one magnitude smaller than the bottom ash flow. A different ENM distribution was found for CNTs that are expected to burn to a large extent (94%) so that only insignificant amounts remain in the system. The results of the modeling show that waste incineration can have a strong influence on some ENM but that still the majority of the ENM-mass is expected to end up in landfills.

Aggregate morphology of nano-TiO2: role of primary particle size, solution chemistry, and organic matter

Abstract: A systematic investigation was conducted to understand the role of aquatic conditions on the aggregate morphology of nano-TiO2, and the subsequent impact on their fate in the environment. In this study, three distinctly sized TiO2nanoparticles (6, 13, and 23 nm) that had been synthesized with flame spray pyrolysis were employed. Nanoparticle aggregate morphology was measured using static light scattering (SLS) over a wide range of solution chemistry, and in the presence of natural organic matter (NOM). Results showed that primary nanoparticle size can significantly affect the fractal dimension of stable aggregates. A linear relationship was observed between surface areas of primary nanoparticles and fractal dimension indicating that smaller primary nanoparticles can form more compact aggregate in the aquatic environment. The pH, ionic strength, and ion valence also influenced the aggregate morphology of TNPs. Increased pH resulted a decrease in fractal dimension, whereas higher ionic strength resulted increased fractal dimension particularly for monovalent ions. When NOM was present, aggregate fractal dimension was also affected, which was also notably dependent on solution chemistry. Fractal dimension of aggregate increase for 6 nm system in the presence of NOM, whereas a drop in fractal dimension was observed for 13 nm and 23 nm aggregates. This effect was most profound for aggregates comprised of the smallest primary particles suggesting that interactions of NOM with smaller primary nanoparticles are more significant than those with larger ones. The findings from this study will be helpful for the prediction of nanoparticle aggregate fate in the aquatic environment.

Environmental contamination and human exposure to dioxin-related compounds in e-waste recycling sites of developing countries

Abstract: E-waste recycling using uncontrolled processes is a major source of dioxin-related compounds (DRCs), including not only the regulated polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) but also non-regulated brominated and mixed halogenated compounds (PBDD/Fs and PXDD/Fs). Various studies at informal e-waste recycling sites (EWRSs) in Asian developing countries found the soil contamination levels of PCDD/Fs from tens to ten thousand picogram TCDD-equivalents (TEQ) per gram and those of DL-PCBs up to hundreds of picogram TEQ per gram. The air concentration of PCDD/Fs was reported as high as 50 pg TEQ per m3 in Guiyu, the largest Chinese EWRS. Non-regulated compounds also contributed substantially to the total DL toxicity of the DRC mixtures from e-waste, as evidenced by the high TEQ levels estimated for the currently identifiable PBDD/Fs as well as the large portion of unexplained bioassay-derived TEQ levels in soils/dusts from EWRSs. Considering the high exposure levels estimated for EWRS residents, especially children, comprehensive emission inventories of DRCs from informal e-waste recycling, the identities and toxic potencies of unidentified DRCs released, and their impacts on human health need to be investigated in future studies.

Levels and distribution of polybrominated diphenyl ethers in soil, sediment and dust samples collected from various electronic waste recycling sites within Guiyu town, southern China

Abstract: Electronic waste recycling operations in some parts of Asia are conducted using rudimentary techniques which result in workplace and environmental contamination with toxic metals and persistent organic pollutants. This study reports concentrations of 14 polybrominated diphenyl ethers (PBDEs), from tri- to deca-brominated, in 31 samples of soil, sediment, dust or ash collected in the vicinity of e-waste recycling sites in Guiyu (southeast China) which were engaged in common activities such as dismantling, shredding, solder recovery, acid processing and open burning. The concentrations detected in this study far exceed those reported previously in urban soil and sediment and are consistent with or exceed those reported in previous studies around e-waste processing facilities. Some of the highest PBDE concentrations reported to date (e.g. 390 000 ng g−1 dw (∑ 14 PBDEs)) were found in a sample collected from a site used for open-burning of e-waste, while an average concentration of 220 000 ng g−1 dw (∑ 14 PBDEs) occurred in sediments impacted by circuit board shredding. A decrease in PBDE concentrations observed with increasing distance from workshops in samples associated with acid processing of wastes provides evidence that such operations are a significant source of PBDEs to the environment. Principal components analysis reveals a complex PBDE congener distribution, suggesting contamination by two or even three commercial formulations consistent with the diverse range of wastes processed.

Nanomaterial disposal by incineration

Abstract: As nanotechnology-based products enter into widespread use, nanomaterials will end up in disposal waste streams that are ultimately discharged to the environment. One possible end-of-life scenario is incineration. This review attempts to ascertain the potential pathways by which nanomaterials may enter incinerator waste streams and the fate of these nanomaterials during the incineration process. Although the literature on incineration of nanomaterials is scarce, results from studies of their behavior at high temperature or in combustion environments for other applications can help predict their fate within an incinerator. Preliminary evidence suggests nanomaterials may catalyze the formation or destruction of combustion by-products. Depending on their composition, nanomaterials may undergo physical and chemical transformations within the incinerator, impacting their partitioning within the incineration system (e.g., bottom ash, fly ash) and the effectiveness of control technology for removing them. These transformations may also drastically affect nanomaterial transport and impacts in the environment. Current regulations on incinerator emissions do not specifically address nanomaterials, but limits on particle and metal emissions may prove somewhat effective at reducing the release of nanomaterials in incinerator effluent. Control technology used to meet these regulations, such as fabric filters, electrostatic precipitators, and wet electrostatic scrubbers, are expected to be at least partially effective at removing nanomaterials from incinerator flue gas.

Heavy metals and organic compounds contamination in soil from an e-waste region in South China

Abstract: Heavy metals and persistent organic pollutants polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were analyzed in 34 surface soil samples collected from farmland and 7 soil or dust samples collected from the workshops in South China, where e-waste was dismantled using primitive techniques. The results show that Cd, Cu and Hg were the most abundant metals, in particular Cd pollution was serious in farmland soils, and the median concentrations in farmland soils were beyond the environmental quality standard for soils (China Grade II). A correlation between Cd, Cu, Zn, Pb and PCBs or PBDEs was significant indicating similar sources. Among the PCB congeners, high relative similarity was observed between the e-waste dump site soil (EW1) and Aroclor 1254, implying that the technical product Aroclor 1254 was one of the major sources of PCB contamination. High concentrations of PCBs in workshop dusts (D2 and D3) (1958 and 1675 μg kg(-1)) demonstrated that the workshops dismantling electrical wires and cables, electrical motors, compressors and aluminum apparatus containing PCBs in lubricants represent strong PCB emission sources to this area. Principal component analysis (PCA) and PBDE homologue patterns verify that farmland soils surrounding the e-waste recycling sites were enriched with lower brominated congeners, and the major source of PBDEs in dust samples might potentially be associated with the extensive use of deca-mix technical products as a flame retardant. The difference between e-waste soils, dusts and farmland soils can be observed in the PCA score plot of PCBs and PBDEs, and E-waste soils and dusts exhibited more diversity than farmland soils. Furthermore, a prediction of the particular kinds of pollution from different recycling activities through the analysis of each contamination and the connections between them was investigated.

Biovolatilisation: a poorly studied pathway of the arsenic biogeochemical cycle

Abstract: It has been known for over a hundred years that microorganisms can produce volatile arsenic (As) species, termed “arsines”. However, this topic has received relatively little attention compared to As behaviour in soils and biotransformation through the trophic level in the marine and terrestrial environment. We believe this is due to long-standing misconceptions regarding volatile As stability and transport as well as an absence, until recently, of appropriate sampling methods. First and foremost, an attempt is made to unify arsines' designations, notations and formulas, taking into account all the different terms used in the literature. Then, the stability of As volatile species is discussed and new analytical developments are explored. Further, the special cases of diffuse low-level emissions (e.g. soil and sediment biovolatilisation), and point sources with high-level emissions (geothermal environments, landfills, and natural gas) are comprehensively reviewed. In each case, future possible areas of research and unknown mechanisms are identified and their importance towards the global As biogeochemical cycle is explored. This review gathers new information regarding mechanisms, stability, transport and sampling of the very elusive arsines and shows that more research should be conducted on this important process.

The impact of PFOS on health in the general population: a review

Abstract: Perfluorooctane sulphonate (PFOS) is a persistent organic pollutant that is toxic, bioaccumulative and undergoes wide transportation across all environmental media. It has been widely detected in environmental samples but there is limited information about the health effects on humans from environmental exposure. This paper presents the findings of a review of the literature on the impact of PFOS on the health of the general population. Fifteen relevant epidemiological studies were identified that looked at the association between human PFOS exposure and a range of health related outcomes. Small but statistically significant associations have been reported with PFOS and total cholesterol, glucose metabolism, body mass index (BMI), thyroid function, infertility, breast feeding, uric acid and attention deficit/hyperactivity disorder (ADHD). The true significance of these findings is uncertain due to the inconsistencies in some of the study results and the limitations of the literature. The majority of studies were cross-sectional and considered surrogate markers of health (e.g. cholesterol levels). The available literature is also limited in ascertaining the link between PFOS concentrations in the environment, exposure pathways and health effects. We conclude that the current evidence is inconclusive and further large-scale prospective cohort studies would be useful to assess the association between environmental exposure to PFOS, appropriate biomarkers (e.g. serum levels of PFOS) and health outcomes.

Seasonal and spatial variability in chemical composition and mass closure of ambient ultrafine particles in the megacity of Los Angeles

Abstract: Emerging toxicological research has shown that ultrafine particles (UFP, dp < 0.1–0.2 μm) may be more potent than coarse or fine particulate matter. To better characterize quasi-UFP (PM0.25, dp < 0.25 μm), we conducted a year-long sampling campaign at 10 distinct areas in the megacity of Los Angeles, including source, near-freeway, semi-rural receptor and desert-like locations. Average PM0.25 mass concentration ranged from 5.9 to 16.1 μg m−3 across the basin and over different seasons. Wintertime levels were highest at the source site, while lowest at the desert-like site. Conversely, summertime concentrations peaked at the inland receptor locations. Chemical mass reconstruction revealed that quasi-UFP in the basin consisted of 49–64% organic matter, 3–6.4% elemental carbon, 9–15% secondary ions (SI), 0.7–1.3% trace ions, and 5.7–17% crustal material and trace elements, on a yearly average basis. Organic carbon (OC), a major constituent of PM0.25, exhibited greatest concentrations in fall and winter at all sites, with the exception of the inland areas. Atmospheric stability conditions and particle formation favored by condensation of low-volatility organics contributed to these levels. Inland, OC concentrations peaked in summer due to increased PM0.25 advection from upwind sources coupled with secondary organic aerosol formation. Among SI, nitrate peaked at semi-rural Riverside sites, located downwind of strong ammonia sources. Moreover, ionic balance indicated an overall neutral quasi-UFP aerosol, with somewhat lower degree of neutralization at near-freeway sites in winter. Anthropogenic metals peaked at the urban sites in winter while generally increased at the receptor areas in summer. Lastly, coefficients of divergence analysis showed that while PM0.25 mass is relatively spatially homogeneous in the basin, some of its components, mainly EC, nitrate and several toxic metals, are unevenly distributed. These results suggest that population exposure to quasi-UFP can substantially vary by season and over short spatial scales in the megacity of Los Angeles.

Real-time particle monitor calibration factors and PM2.5 emission factors for multiple indoor sources

Abstract: Indoor sources can greatly contribute to personal exposure to particulate matter less than 2.5 μm in diameter (PM2.5). To accurately assess PM2.5 mass emission factors and concentrations, real-time particle monitors must be calibrated for individual sources. Sixty-six experiments were conducted with a common, real-time laser photometer (TSI SidePak™ Model AM510 Personal Aerosol Monitor) and a filter-based PM2.5 gravimetric sampler to quantify the monitor calibration factors (CFs), and to estimate emission factors for common indoor sources including cigarettes, incense, cooking, candles, and fireplaces. Calibration factors for these indoor sources were all significantly less than the factory-set CF of 1.0, ranging from 0.32 (cigarette smoke) to 0.70 (hamburger). Stick incense had a CF of 0.35, while fireplace emissions ranged from 0.44–0.47. Cooking source CFs ranged from 0.41 (fried bacon) to 0.65–0.70 (fried pork chops, salmon, and hamburger). The CFs of combined sources (e.g., cooking and cigarette emissions mixed) were linear combinations of the CFs of the component sources. The highest PM2.5 emission factors per time period were from burned foods and fireplaces (15–16 mg min−1), and the lowest from cooking foods such as pizza and ground beef (0.1–0.2 mg min−1).

Molecular toxicology of polybrominated diphenyl ethers: nuclear hormone receptor mediated pathways

Abstract: Polybrominated diphenyl ethers (PBDEs) are used in large quantities as flame retardant additives in commercial products. Bio-monitoring data show that PBDE concentrations have increased rapidly in the bodies of wildlife and human over the last few decades. Based on the studies on experimental animals, the toxicological endpoints of exposure to PBDEs are likely to be thyroid homeostasis disruption, neuro-developmental deficits, reproductive ineffectiveness and even cancer. Unfortunately, the available molecular toxicological evidence for these endpoints is still very limited. This review focuses on the recent studies on the molecular mechanisms of PBDE toxicities carried out through the hormone receptor pathways, including thyroid hormone receptor, estrogen receptor, androgen receptor, progesterone receptor and aryl hydrocarbon receptor pathways. The general approach in the mechanistic investigation is to examine the in vitro direct binding of a PBDE with a receptor, the in vitro recruitment of a co-activator or co-repressor by the ligand-bound receptor, and the participation of the ligand in the receptor-mediated transcription pathways in cells. It is hoped that further studies in this area would provide more insights into the potential risks of PBDEs to human health.

Detection of single walled carbon nanotubes by monitoring embedded metals

Abstract: Detection of single walled carbon nanotubes (CNTs) was performed using single particle-inductively coupled plasma-mass spectrometry (spICPMS). Due to the ambiguities inherent in detecting CNTs by carbon analysis, particularly in complex environmental matrices, this study focuses on using trace catalytic metals intercalated in the CNT structure as proxies for the nanotubes. Using a suite of commercially available CNTs, the monoisotopic elements Co and Y were found to be the most effective for differentiation of particulate pulses from background. The small, variable, amount of trace metal in each CNT makes separation from instrumental background challenging; multiple cut-offs for determining CNT number concentration were investigated to maximize the number of CNTs detected and minimize the number of false positives in the blanks. In simple solutions the number of CNT pulses detected increased linearly with concentration in the ng L−1 range. However, analysis of split samples by both spICPMS and Nanoparticle Tracking Analysis (NTA) showed the quantification of particle number concentration by spICPMS to be several orders of magnitude lower than by NTA. We postulate that this is a consequence of metal content and/or size, caused by the presence of many CNTs that do not contain enough metal to be above the instrument detection limit, resulting in undercounting CNTs by spICPMS. However, since the detection of CNTs at low ng L−1 concentrations is not possible by other techniques, spICPMS is still a more sensitive technique for detecting the presence of CNTs in environmental, materials, or biological applications. To highlight the potential of spICPMS in environmental studies the release of CNTs from polymer nanocomposites into solution was monitored, showcasing the technique's ability to detect changes in released CNT concentrations as a function of CNT loading.