Structural and functional vulnerability to elevated pCO2 in marine benthic communities

The effect of elevated pCO₂/low pH on marine invertebrate benthic biodiversity, community structure and selected functional responses which underpin ecosystem services (such as community production and calcification) was tested in a medium-term (30 days) mesocosm experiment in June 2010. Standardised intertidal macrobenthic communities, collected (50.3567°N, 4.1277°W) using artificial substrate units (ASUs), were exposed to one of seven pH treatments (8.05, 7.8. 7.6, 7.4, 7.2, 6.8 and 6.0). Community net calcification/dissolution rates, as well as changes in biomass, community structure and diversity, were measured at the end of the experimental period. Communities showed significant changes in structure and reduced diversity in response to reduced pH: shifting from a community dominated by calcareous organisms to one dominated by non-calcareous organisms around either pH 7.2 (number of individuals and species) or pH 7.8 (biomass). These results were supported by a reduced total weight of CaCO₃ structures in all major taxa at lowered pH and a switch from net calcification to net dissolution around pH 7.4 (Ω_calc = 0.78, Ω_ara = 0.5). Overall community soft tissue biomass did not change with pH and high mortality was observed only at pH 6.0, although molluscs and arthropods showed significant decreases in soft tissue. This study supports and refines previous findings on how elevated pCO₂ can induce changes in marine biodiversity, underlined by differential vulnerability of different phyla. In addition, it shows significant elevated pCO₂-/low pH-dependent changes in fundamental community functional responses underpinning changes in ecosystem services.     

Equilibration time scales of organic aerosol inside thermodenuders: Evaporation kinetics versus thermodynamics

The interpretation of thermodenuder (TD) data often relies on the assumption that thermodynamic equilibrium is reached inside the instrument. We modeled the evaporation of three organic aerosol types (adipic acid, α-pinene SOA and aged OA) inside a thermodenuder with a mass transfer model, and calculated equilibration time scales for these systems at realistic conditions. The equilibrium times varied from less than a second to several hours, decreasing with increasing aerosol concentrations, decreasing particle sizes, decreasing volatilities and increasing mass accommodation coefficients. The results indicate that generally TDs measure particle evaporation rates rather than equilibria, and time-dependent modeling of the evaporation is usually needed to interpret the data. Measurements at varying residence times and temperatures, on the other hand, are desirable to investigate the equilibration of the studied aerosol and decouple the kinetic effects from the effects caused by the thermodynamic properties of the aerosol. Organic aerosol is likely to be further from equilibrium under typical field conditions compared with laboratory data. When determining the aerosol properties from TD data, assuming incorrectly equilibrium results in under-prediction of the vaporization enthalpy of the evaporating species. Similar under-estimation is predicted if multicomponent aerosols are approximated with single-component properties.     

Ambient TSP concentration and dustfall in major cities of China: Spatial distribution and temporal variability

Based on environmental monitoring data in 93 major cities and meteorological records at 398 weather stations in China from 1981 to 2007, total suspended particle (TSP) concentration, the intensity of dustfall, and sand and dust storm frequency (F_d) were analysed. During the past 27 years, the annual average TSP concentration (C_TSP) in 93 cities was 402 μg m^?3. Annual average C_TSP decreased from the north to the south and from inland to the coast areas with a peak value of 628.8 μg m^?3 in Lanzhou. In the 1980s, 1990s and 2000s, annual average C_TSP was 628.7, 319.2, and 250.1 μg m^?3, respectively. Annual average intensity of dustfall (I_d) was 240.5 t km^?2 a^?1, decreased from northern to southern China and from inland to the coast areas with the maximum value of 717.2 t km^?2 a^?1 in Baotou. In the 1980s, 1990s and 2000s, annual average I_d was 334.8, 220.9, 146 t km^?2 a^?1 respectively. Annual average I_d in the Loess Plateau region was commonly higher than 200 t km^?2 a^?1. The annual average F_d decreased from arid regions in northwestern China to humid areas in southeastern China with two sand and sand storm centers existing in Xinjiang Taklamakan Desert and western Inner Mongolia. The annual average F_d in the 1980s, 1990s, 2000s was 16, 8, 6 days respectively, decreased steadily from 18 days in 1981–5 days in 2007. Annual average I_d had a positive linear relation to annual average C_TSP (R² = 0.96). Annual average F_d had a positive relation with annual average C_TSP (R² = 0.97) as well as annual average I_d (R² = 0.94). TSP was the chief pollutant influencing Air Pollution Index (API) in northern China in spring and winter seasons. Sand and dust storm might be a major factor affecting the temporal variability and spatial distribution of TSP and dustfall in China.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

PM2.5 and PM10: The influence of sugarcane burning on potential cancer risk

In Brazil, sugarcane fields are often burned to facilitate manual harvesting, and this burning causes environmental pollution from the large amounts of soot released into the atmosphere. This material contains numerous organic compounds such as PAHs. In this study, the concentrations of PAHs in two particulate-matter fractions (PM_2.5 and PM₁₀) in the city of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugarcane plantations) were determined during the sugarcane harvest (HV) and non-harvest (NHV) seasons in 2008 and 2009. The sampling strategy included four campaigns, with 60 samples in the NHV season and 220 samples in the HV season. The PM_2.5 and PM₁₀ fractions were collected using a dichotomous sampler (10 L min^?1, 24 h) with Teflon? filters. The filter sets were extracted (ultrasonic bath with hexane/acetone (1:1 v/v)) and analyzed by HPLC/Fluorescence. The median concentration for total PAHs (PM_2.5 in 2009) was 0.99 ng m^?3 (NHV) and 3.3 ng m^?3 (HV). In the HV season, the total concentration of carcinogenic PAHs (benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene) was 5 times higher than in the NHV season. B(a)P median concentrations were 0.017 ng m^?3 and 0.12 ng m^?3 for the NHV and HV seasons, respectively. The potential cancer risk associated with exposure through inhalation of these compounds was estimated based on the benzo[a]pyrene toxic equivalence (BaP_eq), where the overall toxicity of a PAH mixture is defined by the concentration of each compound multiplied by its relative toxic equivalence factor (TEF). BaP_eq median (2008 and 2009 years) ranged between 0.65 and 1.0 ng m^?3 and 1.2–1.4 ng m^?3 for the NHV and HV seasons, respectively. Considering that the maximum permissible BaP_eq in ambient air is 1 ng m^?3, related to the increased carcinogenic risk, our data suggest that the level of human exposure to PAHs in cities surrounded by sugarcane crops where the burning process is used is cause for concern.     

Relation between extracellular polymers' composition and its ability to complex Cd,Cu and Pb

Activated sludges originated from wastewater treatment plants (WWTPs) play an important role in heavy metal removal from effluents. Extracellular polymers (ECP) form a major part of the activated sludge and are heavily involved in biosorption of heavy metals. The complexation of three heavy metals (Cd, Cu and Pb) with ECP extracted from six activated sludges, originated from different WWTPs, was investigated at pH 7.

ECP in the study were shown to be mainly composed of proteins, humic acids, uronic acids and polysaccharides along with smaller amounts of lipids and nucleic acids. IR spectra confirmed the presence of the functional groups usually found in the ECP and the content in each fraction was determined using colorimetric methods. The determination of surface charge was carried out on each ECP sample and allowed two pK_a values characteristic of two distinctive functional groups to be determined. At the pH used in the study, the value of these constants indicates that only one functional group is under protonated form.

A polarographic method was used to determine the complexation parameters (number of binding sites and complexation constant) of ECP solutions towards metals. The following orders were established for the number of binding sites: Cu > Pb  Cd and for the stability of the ECP–metal complex: Cd > Pb  Cu.

A matrix of correlation between the composition of the polymers and the complexation parameters showed that the number of binding sites and the complexation constant were strongly linked to proteins, polysaccharides and humic substances content.     

The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.     

Generation and stability of bentonite colloids at the bentonite/granite interface of a deep geological radioactive waste repository

The possible mechanisms of colloid generation at the near field/far field interface of a radioactive repository have been investigated by means of novel column experiments simulating the granite/bentonite boundary, both in dynamic and in quasi-static water flow conditions. It has been shown that solid particles and colloids can be detached from the bulk and mobilised by the water flow. The higher the flow rate, the higher the concentration of particles found in the water, according to an erosion process. However, the gel formation and the intrinsic tactoid structure of the clay play an important role in the submicron particle generation even in the compacted clay and in a confined system. In fact, once a bentonite gel is formed, in the regions where the clay is contacted with water, clay colloids can be formed even in quasi-static flow conditions. The potential relevance of these colloids in radionuclide transport has been studied by evaluating their stability in different chemical environments. The coagulation kinetics of natural bentonite colloids was experimentally studied as a function of the ionic strength and pH, by means of time-resolved light scattering techniques. It has been shown that these colloids are very stable in low saline (approximately 1 x 10(-3) M) and alkaline (pH > or = 8) waters.     

Sorption of As(V) ions by akaganéite-type nanocrystals

A priority pollution problem, the removal of arsenate oxyanions from dilute aqueous solutions by sorption onto synthetic akaganéite (beta-FeO(OH)) was the aim of the present study. This is an innovative inorganic adsorbent material prepared in the laboratory, following a new method of preparation. The effect of akaganéite and arsenate concentration, the contact time, temperature, solution pH value, and ionic strength variation on the treatment process was mainly investigated during this study. Typical adsorption isotherms were determined, which were found to fit sufficiently the typical Langmuir equation. The mechanism of sorption was examined by electrokinetic, X-ray diffraction, Fourier transmission infrared and scanning electron microscopy measurements. Promising results were obtained, due to the favourite characteristics of the adsorbent applied.     

Metal ion removal from water by sorption on paper mill sludge

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.