Separation and remediation of environmental pollutants using metal–organic framework-based tailored materials

Environmental Science and Pollution Research - Metal–organic frameworks (MOFs) are a polymer hybrid family of compounds comprising metal ions that have been deliberately incorporated in...     

Do tubificid worms influence the fate of organic matter and pollutants in stormwater sediments?

In urban area, management of stormwater leads to the accumulation of polluted sediments at the water-sediment interface of various aquatic ecosystems. In many cases, these sediments are colonised by dense populations of tubificid worms. However, the influence of tubificid worms on the fate of stormwater sediments has never been tackled. The aim of this study was to measure in sediment columns the influence of tubificid worms on sediment reworking, organic matter processing (O(2) uptake and release of NH(4)(+), NO(3)(-), PO(4)(3-), and dissolved organic carbon), release of hydrocarbons and heavy metals, and microbial characteristics. Results showed that tubificid worms increased the release of NH(4)(+), PO(4)(3-), and dissolved organic carbon by 2-, 4-, and 3-fold, respectively. O(2) uptake also increased by more than 35% due to tubificid activity. The increase in the percentages of active bacteria and hydrolytic activity in the presence of worms indicated that the higher sediment respiration was caused by the stimulation of microbial communities. A reduction of the number of sulphate-reducing bacteria in the uppermost layers of the sediment was attributed to the penetration of O(2) due to worm activity. These significant effects of tubificid worms were probably linked to the dense network of burrows, which enhanced the exchange surface between the water column and the sediment. No release of heavy metals and hydrocarbons to the water phase was detected in the sediment columns. Understanding the fate and effect of organic stormwater sediments in the natural environment requires the integration of the role of bioturbation in urban pollution studies.     

Temporal trends of lipophilic persistent organic pollutants in serum from Danish nulliparous pregnant women 2011–2013

The use of the lipophilic persistent organic pollutants (POPs) including polychlorinated biphenyls (PCBs) and several organochlorine pesticides (OCPs) has been prohibited for more than 30 years. In this study, we present the temporal trends of the lipophilic POP serum concentrations in Danish nulliparous pregnant women between 2011 and 2013. We randomly selected 197 pregnant women (gestational age 11–13) from the Aarhus Birth Cohort. The concentrations of the lipophilic POPs in the serum samples were analyzed using gas chromatography. The concentrations were corrected for total serum lipids. The statistical analysis was performed by regression analysis with adjustment for age, BMI, gestational age at blood draw, and smoking status. The serum concentrations of PCB 118, 138, 153, 156, 170, 180, 187, and hexachlorobenzen, trans-nonachlor, β-hexachlorocyclohexane (β-HCH), and p,p’-dichlorodiphenyldichloroethylene were lower in 2013 than in 2011. However, the oxychlordane concentration was lowest in 2011. The serum levels of most lipophilic POPs followed downward trends during the study period, which was expected, as these compounds has been banned for many years. The upward trend of oxychlordane was unexpected and presumably a chance finding.     

Gas–particle partitioning of persistent organic pollutants in the Western Balkan countries affected by war conflicts

Background, aim, and scope  

Bombing and destruction of the industrial and military targets accompanied by complete or incomplete combustion during the war conflict and NATO operation in former Yugoslavia caused the emission of persistent organic pollutants into the atmosphere, water, and soil. A total of 129 ambient air samples from 24 background, urban, and industrial sites, including hot spots, were collected to assess a gas–particle partitioning behavior of various persistent organic pollutants.     

Monitoring of persistent organic pollutants (POPs): examples from Lake Vättern, Sweden

Lake V?ttern in southern Sweden is a large oligotrophic lake with high surface to catchment area ratio (ca. 0.4) and a water residence time of 60 years. The lake combines sensitivity to atmospheric POP-pollution with general susceptibility for effects of POPs and slow concentration decline. Time series, from the 1960s until 1996, of PCBs and DDT in fish and data on TCDD in sediment of L. V?ttern are presented and compared to other large lakes. The long time dataset of POPs in Arctic char (Salvelinus salvelinus) shows a significant annual decline of about 5% for PCBs and 13% for DDT. These rates are in agreement with other studies. Nutrients as well as biological effects and factors affecting the fate of POPs in oligotrophic lakes with long residence times are discussed. We propose that oligotrophic clear lakes are important ecosystems for monitoring POPs in biota.     

Effects of unregulated anthropogenic activities on mixing ratios of volatile organic air pollutants—A case study

During the months of October to November, many important festivals are celebrated in India. Celebration of these festivals are marked by extensive use of fireworks or pyrotechnics, bonfire, incense burning, open air community cooking, and temporary eateries using crude fuel such as coal, wood, kerosene, cow dung, burning of raw/semiwood, and coconut shells. The present study deals with the influence of these unregulated anthropogenic activities on ambient mixing level of volatile organic compounds (VOCs), especially some carbonyl compounds. The study was undertaken in the metropolitan city of Kolkata, India, with very high population density, which is even higher during festival period. The average total carbonyl level at different sites in Kolkata varied from 134.8 to 516.5 μg m^?3 in pre-festival season, whereas in post-festival season the same varied from 252.2 to 589.3 μg m^?3. Formaldehyde to acetaldehyde ratio altered from 0.62 in pre-festival season to 1.78 in post-festival season. Diurnal variation also altered, indicating variation in source composition of carbonyls. The total ozone forming potential calculated for all 14 carbonyls in pre-festival season increased by 35% in post-festival season. The effect of anthropogenic activities typical to the event of Diwali night characterized by intense execution of pyrotechnics resulted in significantly high level of carbonyl VOCs. Principal component analysis study for the event of Diwali shows clear contribution of the event on certain carbonyl VOCs. The results indicate elevated primary emissions of these pollutants and also their effect on formation of secondary pollutants. The study emphasizes the need of generating awareness among the communities in society as well as need for regulations to minimize the emissions and related hazards to the extent possible.

Implications: Altered anthropogenic activities typical of festival season including extensive use of pyrotechnics affect ambient level of volatile organic compounds, especially some carbonyls. Such activities have considerable effect on interspecies ratio and diurnal variation. They also affect formation of secondary pollutants such as tropospheric ozone. Principal component analysis (PCA) study shows clear contribution of the pyrotechnics execution on certain carbonyl VOCs. The findings emphasize the need of generating awareness in society and need for regulations to minimize the emissions.     

Do tubificid worms influence organic matter processing and fate of pollutants in stormwater sediments deposited at the surface of infiltration systems?

The purpose of this study was to quantify the influences of tubificid worms on the biogeochemical functioning of an infiltration system impacted by a stormwater sediment deposit. Effects of worms with stormwater sediment deposit were compared with effects of worms with two other natural sediment deposits (one low and one rich-particulate organic matter deposits). We measured the effects of invertebrates on sediment reworking, organic matter processing, solute fluxes, microbial characteristics, and pollutant release from stormwater deposit to water. Our results showed that tubificid worms had slight effects on microbial activities in presence of the stormwater deposit whereas they significantly stimulated microbial activities in columns impacted by the other two deposits. High contents of labile organic matter contained in stormwater sediments probably led to very strong microbial activities that could not be easily stimulated by worm activities. In our experimental conditions, no significant influence of tubificid worms on the fate of pollutants (heavy metals and PAHs) contained in the stormwater deposit was measured. In conclusion, our study demonstrated that the organic matter characteristics of the stormwater sediments limited the efficiency of tubificid worms to stimulate organic matter mineralization in infiltration systems.     

Titanium dioxide and graphitic carbon nitride–based nanocomposites and nanofibres for the degradation of organic pollutants in water: a review

Environmental Science and Pollution Research - The paper reviews graphitic carbon nitride–based nanostructured photocatalytic materials and nanofibres for applications in water purification....     

Persistent organic pollutants associated to water fluxes and sedimentary processes in the Colorado River delta, Baja California, México

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were studied in sediment cores from two distinctive modern channels of the Colorado River (CR) delta. Their abundance and temporal changes are associated with flood-flows from the CR across the USA-Mexico border. The CR channel is directly exposed to river flood-flows while the Hardy River (HR) is a local channel derived mainly from agricultural runoff, geothermal effluents, and treated urban wastewater. Different headwater compositions and degrees of exposure to flood-flows appear to be the factors controlling the composition of persistent organic pollutants (POPs). Enrichment of OCPs (46 ng g⁻¹ dwt in HR and 4.37 ng g⁻¹ dwt in CR) occurred during or a few years after flooding. PCB-138 (4.2 ng g⁻¹ dwt) is enriched in HR suggesting its origin in dielectric oils from the geothermal power plant. PCB-28 (2.1 ng g⁻¹ dwt) in CR may be related with atmospheric input and/or re-deposition of upstream sediments. In surficial sediments (0-3 cm), only HR exceeds international sediment quality guidelines (4,4′-DDE = 8.16 ng g⁻¹ dwt and ΣDDT = 8.34 ng g⁻¹ dwt).     

Predicting logarithmic values of the subcooled liquid vapor pressure of halogenated persistent organic pollutants with QSPR: How different are chlorinated and brominated congeners?

Logarithmic values of the subcooled liquid vapor pressure (log P_L) were estimated for 1436 polychlorinated and polybrominated congeners of benzenes, biphenyls, dibenzo-p-dioxins, dibenzofurans, diphenyl ethers and naphthalenes by employing the Quantitative Structure–Property Relationships (QSPR) approach. The QSPR model developed with GA–PLS technique was characterized by satisfactory goodness-of-fit, robustness and the external predictive performance (R²Y = 0.970, Q_CV² = 0.970, Q_Ext² = 0.966, RMSE_C = 0.21, RMSE_CV = 0.22 and RMSE_P = 0.22). The externally validated model has been applied to predict subcooled liquid vapor pressure of uninvestigated halogenated persistent organic pollutants. Moreover, a simple arithmetic relationship between logarithmic values of subcooled liquid vapor pressures in pairs of chloro- and bromo-analogues has been found. This relationship can be used for estimating log P_L of a brominated compound, whenever log P_L of its chlorinated counterpart is known, without necessity of performing any time-consuming computations.     

Historical trends in persistent organic pollutants and metals recorded in sediment from Lake Ellasjøen, Bjørnøya, Norwegian Arctic

Ellasj?en receives contaminants from both atmospheric and biological transport (seabird guano). Historical trends of selected persistent organic pollutants and metals were determined by interpretation of down-core contaminant profiles in conjunction with sediment layer ages, determined by the (210)Pb method. Polychlorinated biphenyls (PCBs) and dichloro-diphenyl-trichloroethane and metabolites (DDTs) increased from about 1930 until 1970 (max. sum PCBs 71.8 ng/g dry weight (dw), max sum DDTs 4.0 ng/g dw), declining afterwards to 46.4 ng/g dw and 1.6 ng/g dw, respectively. Polybrominated diphenylethers (PBDEs) concentrations are increasing in Ellasj?en, reaching 0.73 ng/g dw in 2001. Hexabromocyclododekane (HBCD) was measured only in sediment from 1-2 cm depth (0.43 and 3.88 ng/g dw of alpha- and gamma-HBCD, respectively). Most metals (As, Cd, Co, Ni and Zn) showed a similar pattern as PCBs. No clear trends were observed for Cr, Pb or V. Mercury (Hg) has increased gradually since the beginning of the industrial era.     

Atmospheric pollutants and ectomycorrhizae: more questions than answers?

Changes in research emphasis from pollution towards the effects of climate change have resulted from shifts in political and public interests. Information gained from research on the effects of pollutants as a perturbation on mycorrhizae and mycorrhizae-mediated processes may be an appropriate starting point from which to launch into climate change studies. However, the effects of pollution on mycorrhizae are not clear cut as there are many conflicting results. The methods used in experiments, levels of pollutants used and relationships between studies on seedling trees to the mature forest do not suggest unifying models of pollution effects. Some areas of work still lacking in the pollution field are highlighted. These include well replicated experiments at currently ambient pollutant levels, and areas for potential development in the global climate change arena, e.g. the interaction between C supply and nutrient uptake.     

Biomarker responses in European eel (Anguilla anguilla) exposed to persistent organic pollutants. A field study in the Vaccarès lagoon (Camargue, France)

A screening of relevant biomarkers was carried out in order to evaluate metabolic and cellular damages in European eels exposed to a non-point source contamination by persistent organic pollutants (POP) such as polycyclic aromatic hydrocarbons (PAH) and organochlorine compounds (OC) in a protected area, the Nature Reserve of Camargue (France). Investigations were focused on metabolic responses including detoxification mechanisms (biotransformation, antioxidant process), energy requirements and enzymatic membrane markers either involved in neuronal conduction (acetylcholinesterase, AChE) or in osmoregulation and energy metabolism (ATPases). The hepatic and muscular glycogen rates seemed to be suitable biomarkers as well as three hepatic activities involved in the protection against oxyradicals: catalase, glutathione peroxidase (SeGPx) and superoxide dismutases (SOD). The muscle and gill ATPases as well as the muscle and brain AChE showed more significant relevance in terms of biomarkers than the biotransformation enzymes: ethoxyresorufine-O-deethylase (EROD) and uridine diphospho-glucuronyl transferase (UDPGT). However, most of these enzymatic activities depend on numerous abiotic factors, which must be taken into account in such a biomarker assessment approach. Our study provides some conclusive elements to approve the use in situ of biomarkers developed from laboratory studies. It also raises a question regarding the location of contaminant impregnation in fish organ, in relation with age, development status or mode of contamination, and its influence on biomarker response. If the relevance of membrane indicators is confirmed, this study provides an original statement of the extent of the ecotoxicological threat for the aquatic species in a protected area, due to the occurrence of POP in the cell membranes.     

Hygroscopic organic aerosols during BRAVO?

The hygroscopic properties of the organic fraction of aerosols are poorly understood. The ability of organic aerosols to absorb water as a function of relative humidity (RH) was examined using data collected during the 1999 Big Bend Regional Aerosol and Visibility Observational Study (BRAVO). (On average, organics accounted for 22% of fine particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) mass). Hourly RH exceeded 80% only 3.5% of the time and averaged 44%. BRAVO aerosol chemical composition and dry particle size distributions were used to estimate PM2.5 light scattering (Bsp) at low and high ambient RH. Liquid water growth associated with inorganic species was sufficient to account for measured Bsp for RH between 70 and 95%.     

EU Water Framework Directive and Stockholm Convention Can we reach the targets for priority substances and persistent organic pollutants?

Background, aim and scope  

Water is a renewable resource and acceptable quality is important for human health, ecological and economic reasons, but human activity can cause great damage to the natural aquatic environment. Managing the water cycle in a sustainable way is the key to protect natural resources and human health. On a global level, the microbiological contamination of water sources is a major problem in connection with poverty and the United Nations Millennium Development Declaration is an important initiative to handle this problem. In terms of environmental health, persistent organic pollutants (POPs) circulate globally; as they travel long distances, they are found in remote areas far from their original source of application and can cause damage wherever they move to. On a global scale, United Nations Environmental Programme (UNEP) issued the Stockholm Convention to reduce POPs; in the European Union (EU), one intention of the Water Framework Directive (WFD) is to reach the good chemical status of waters; beside these regulations, there are other directives in support of these goals. The aim of this paper is to discuss whether the Stockholm Convention and the WFD allows meeting the targets of protection of human and environmental health, which are established in the different directives and how could we approach the targets.     

Polychlorinated camphenes (toxaphenes), polybrominated diphenylethers and other halogenated organic pollutants in glaucous gull (Larus hyperboreus) from Svalbard and Bjørnøya (Bear Island)

The levels of polychlorinated camphenes (toxaphenes) were investigated in liver samples from 18 glaucous gulls (Larus hyperboreus) from Bj?rn?ya (74 degrees N, 19 degrees E) and four individuals from Longyearbyen (78 degrees N, 15 degrees E). Additionally brominated flame retardants (BFRs), PCBs and chlorinated pesticides were investigated in liver and intestinal contents of 15 of the glaucous gulls from Bj?rn?ya. Of the analysed BFRs only 2,2',4,4'-tetra- and 2,2',4,4',5-pentabrominated diphenylethers (PBDE 47 and 99) could be detected. The concentrations ranged between 2 and 25 ng/g ww. In addition, high resolution measurements with GC/HRMS revealed the existence of several, not quantified, PBDEs and polybrominated biphenyls (PBBs) congeners in the samples. B9-1679 and B8-1413 were the dominating toxaphenes with median concentrations of 8 and 15 ng/g ww. Concentrations of toxaphenes and PBDEs were up to 100-times lower than the concentrations of PCB and some of the pesticides. PCB and p,p/-DDE constituted 90% of the contaminants found.     

Forecasting human exposure to atmospheric pollutants in Portugal – A modelling approach

Air pollution has become one main environmental concern because of its known impact on human health. Aiming to inform the population about the air they are breathing, several air quality modelling systems have been developed and tested allowing the assessment and forecast of air pollution ambient levels in many countries. However, every day, an individual is exposed to different concentrations of atmospheric pollutants as he/she moves from and to different outdoor and indoor places (the so-called microenvironments). Therefore, a more efficient way to prevent the population from the health risks caused by air pollution should be based on exposure rather than air concentrations estimations. The objective of the present study is to develop a methodology to forecast the human exposure of the Portuguese population based on the air quality forecasting system available and validated for Portugal since 2005. Besides that, a long-term evaluation of human exposure estimates aims to be obtained using one-year of this forecasting system application. Additionally, a hypothetical 50% emission reduction scenario has been designed and studied as a contribution to study emission reduction strategies impact on human exposure.To estimate the population exposure the forecasting results of the air quality modelling system MM5-CHIMERE have been combined with the population spatial distribution over Portugal and their time-activity patterns, i.e. the fraction of the day time spent in specific indoor and outdoor places. The population characterization concerning age, work, type of occupation and related time spent was obtained from national census and available enquiries performed by the National Institute of Statistics. A daily exposure estimation module has been developed gathering all these data and considering empirical indoor/outdoor relations from literature to calculate the indoor concentrations in each one of the microenvironments considered, namely home, office/school, and other indoors (leisure activities like shopping areas, gym, theatre/cinema and restaurants). The results show how this developed modelling system can be useful to anticipate air pollution episodes and to estimate their effects on human health on a long-term basis. The two metropolitan areas of Porto and Lisbon are identified as the most critical ones in terms of air pollution effects on human health over Portugal in a long-term as well as in a short-term perspective. The coexistence of high concentration values and high population density is the key factor for these stressed areas. Regarding the 50% emission reduction scenario, the model results are significantly different for both pollutants: there is a small overall reduction in the individual exposure values of PM₁₀ (<10 μg m^?3 h), but for O₃, in contrast, there is an extended area where exposure values increase with emission reduction. This detailed knowledge is a prerequisite for the development of effective policies to reduce the foreseen adverse impact of air pollution on human health and to act on time.     

The deep-sea as a final global sink of semivolatile persistent organic pollutants? Part I: PCBs in surface and deep-sea dwelling fish of the north and south Atlantic and the Monterey Bay Canyon (California)

The understanding of the global environmental multiphase distribution of persistent organic pollutants (POPs) as a result of the physico-chemical properties of the respective compounds is well established. We have analysed the results of a vertical transport of POPs from upper water layers (0-200 m) to the deepwater region (> 800 m) in terms of the contamination of the biophase in both water layers. The contents of persistent organochlorine compounds like polychlorinated biphenyls (PCBs) in fish living in the upper water layers of the North Atlantic and the South Atlantic, and at the continental shelf of California (Marine Sanctuary Monterey Bay and its deep-sea Canyon) are compared to the levels in deep-sea or bottom dwelling fish within the same geographic area. The deep-sea biota show significantly higher burdens as compared to surface-living species of the same region. There are also indications for recycling processes of POPs--in this case the PCBs--in the biophase of the abyss as well. It can be concluded that the bio- and geo phase of the deep-sea may act similarly as the upper horizons of forest and grasslands on the continents as an ultimate global sink for POPs in the marine environment.