While chronic acidification of water bodies has been steadily decreasing, episodic acidification continues to affect stream biology by temporarily decreasing pH and mobilizing aluminum. These events are becoming more common as climate change renders more frequent and intense storms and flooding. Throughout Scandinavia the effects of acidification have been mitigated by liming since the 1980ies, but remediation efforts can now be reduced. While transient acidity may reduce fish populations, also other species in streams are affected. In this in-stream study, two macro-invertebrates (Gammarus pulex and Baetis rhodani), both known as salmonid prey organisms, were exposed to snowmelt in six humic brooks with a natural gradient of pH and inorganic monomeric Al (Ali). We hypothesize that acid toxicity thresholds can be defined using lethal (mortality) and sublethal (changes in body elemental content) metrics. Periodic observations were made of mortality and whole body concentrations of base cations (BC: Ca, Mg, Na and K) and metals (Al, Fe, Zn and Mn). Mortality increased dramatically at pH<6.0 and Ali >15 µg/L for G. pulex and at pH<5.7 and Ali >20 µg/L for B. rhodani. No accumulation of Al was found. The invertebrate body Na concentration decreased when pH dropped, suggesting that osmoregulation in both species was affected. In contrast to general BC pattern, Ca concentration in G. pulex and Mg concentration in B. rhodani increased when pH decreased. Although Ali strongly correlates to pH, the Al composition of soil and bedrock also influences Al availability, potentially contributing to toxic Ali episodes. The estimated values calculated in this study can be used to improve water quality criteria and as thresholds to adjust doses of lime compared to old recommendations in ongoing liming programs. Such adjustments may be critical since both Ali and pH levels have to be balanced to mitigate damage to recovering stream ecosystems.
Modelling of pH and inorganic aluminium after termination of liming in 3000 Swedish lakes
Significant resources are spent on counteracting the effects of acidification, mainly by liming. Due to lower S and N deposition in Europe and North America, authorities are changing directives and strategies for remediation and reducing liming. However, as the acid–base buffer capacity differs in different water bodies, the desirable reduction of the lime dose is variable. In this study, a geochemical model is used to predict pH and inorganic monomeric Al (Ali) when liming is reduced and finally terminated in the 3000 Swedish lakes currently treated with lime. To estimate Ca and Mg concentrations not affected by liming for use in the model, the Ca/Mg ratio in nearby unlimed reference lakes was used. For the modelling of pH and inorganic Al the Visual MINTEQ program including the Stockholm Humic Model recently calibrated for Swedish fresh water was used. The predictions were validated with modelling results from six monitored lakes, in which liming had been terminated. The use of geochemical modelling appeared to be a promising tool for the calculation of accurate lime requirements in acid waters. For simulations in which liming was completely terminated, the pH value decreased by, on average, 1 pH unit to pH 5.7, whereas Ali increased by 17 μg L−1 to 32 μg L−1. If liming was reduced by half, the pH would drop only 0.3 pH units and Ali would increase by 2 μg L−1. Lakes in the south-western part of Sweden were predicted to reach a lower pH and higher Ali, which would be expected due to their greater historical S deposition. The results indicate that liming can be terminated in certain areas and in other areas be reduced without increases in the lake acidity.
A High-Volume Cryosampler and Sample Purification System for Bromine Isotope Studies of Methyl Bromide
B.F. Thornton; A. Horst; D. Carrizo; H. Holmstrand; P. Andersson; P.M. Crill; Ö. Gustafsson
| J. Atmos. Ocean. Technol.
A system was developed for collecting from the ambient atmosphere the methyl halides CH3Cl and CH3Br in quantities sufficient for chlorine and bromine isotope analysis. The construction and operation of the novel cryogenic collection system (cryosampler) and sample purification system developed for this task are described. This study demonstrates the capability of the cryosampler by quantifying the CH3Cl and CH3Br collected from atmospheric samples and the nonfractionating bromine isotope fingerprint of CH3Br from synthetic air samples of controlled composition. An optimized cryosampler operation time of 4 h at a flow rate of 15 L min−1 is applied to yield the nearly 40 ng required for subsequent δ81Br-CH3Br analyses. The sample purification system is designed around a packed column gas chromatography–quadropole–mass spectrometry (GCqMS) system with three additional cryotraps and backflushing capacity. The system's suitability was tested by observing both the mass recovery and the lack of Δ81Br isotope fractionation induced during sample purification under varying flow rates and loading scenarios. To demonstrate that the entire system samples and dependably delivers CH3Br to the isotope analysis system without inducing isotope fractionation, diluted synthetic air mixtures prepared from standard gases were processed through the entire system, yielding a Δ81Br-CH3Br of +0.03‰ ± 0.10‰ relative to their starting composition. Finally, the combined cryosampler–purification and analysis system was applied to demonstrate the first-ever δ81Br-CH3Br in the ambient atmosphere with two samples collected in the autumn of 2011, yielding −0.08‰ ± 0.43‰ and +1.75‰ ± 0.13‰ versus standard mean ocean bromide for samples collected at a suburban Stockholm, Sweden, site.
Evaluating the fate of six common pharmaceuticals using a reactive transport model: insights from a stream tracer test
Riml, J.; Wörman, A.; Kunkel, U.; Radke, M.
| Sci. Total Environ.
Quantitative information regarding the capacity of rivers to self-purify pharmaceutical residues is limited. To bridge this knowledge gap, we present a methodology for quantifying the governing processes affecting the fate of pharmaceuticals in streaming waters and, especially, to evaluate their relative significance for tracer observations. A tracer test in Säva Brook, Sweden was evaluated using a coupled physical-biogeochemical model framework containing surface water transport together with a representation of transient storage in slow/immobile zones of the stream, which are presumably important for the retention and attenuation of pharmaceuticals. To assess the key processes affecting the environmental fate of the compounds, we linked the uncertainty estimates of the reaction rate coefficients to the relative influence of transformation and sorption that occurred in different stream environments. The hydrological and biogeochemical contributions to the fate of the pharmaceuticals were decoupled, and the results indicate a moderate hydrological retention in the hyporheic zone as well as in the densely vegetated parts of the stream. Biogeochemical reactions in these transient storage zones further affected the fate of the pharmaceuticals, and we found that sorption was the key process for bezafibrate, metoprolol, and naproxen, while primary transformation was the most important process for clofibric acid and ibuprofen. Conversely, diclofenac was not affected by sorption or transformation.
Temperature-dependent accumulation mode particle and cloud nuclei concentrations from biogenic sources during WACS 2010
Submicron aerosol particles collected simultaneously at the mountain peak (2182 m a.s.l.) and at a forested mid-mountain site (1300 m a.s.l.) on Whistler Mountain,
British Columbia, Canada, during June and July 2010 were analyzed by Fourier transform infrared (FTIR) spectroscopy for quantification of organic functional groups. Positive matrix factorization (PMF) was applied to the FTIR spectra. Three PMF factors associated with (1) combustion, (2) biogenics, and (3) vegetative detritus were identified at both sites. The biogenic factor was correlated with both temperature and several volatile organic compounds (VOCs). The combustion factor dominated the submicron particle mass during the beginning of the campaign, when the temperature was lower and advection was from the Vancouver area, but as the temperature started to rise in early July, the biogenic factor came to dominate as a result of increased emissions of biogenic VOCs, and thereby increased formation of secondary organic aerosol (SOA). On average, the biogenic factor represented 69 % and 49 % of the submicron organic particle mass at Whistler Peak and at the mid-mountain site, respectively. The lower fraction at the mid-mountain site was a result of more vegetative detritus there, and also higher influence from local combustion sources.
The biogenic factor was strongly correlated (r∼0.9) to number concentration of particles with diameter (Dp)>100 nm, whereas the combustion factor was better correlated to number concentration of particles with Dp<100 nm (r∼0.4). The number concentration of cloud condensation nuclei (CCN) was correlated (r∼0.7) to the biogenic factor for supersaturations (S) of 0.2 % or higher, which indicates that particle condensational growth from biogenic vapors was an important factor in controlling the CCN concentration for clouds where S≥0.2 %. Both the number concentration of particles with Dp>100 nm and numbers of CCN for S≥0.2 % were correlated to temperature. Considering the biogenic influence, these results indicate that temperature was a primary factor controlling these CCN concentrations at 0.2 % supersaturation.
Five critical questions of scale for the coastal zone
A large number of processes are involved in the chain from emissions of aerosol precursor gases and primary particles to impacts on cloud radiative forcing. Those processes are manifest in a number of relationships that can be expressed as factors dlnX/dlnY driving aerosol effects on cloud radiative forcing. These factors include the relationships between cloud condensation nuclei (CCN) concentration and emissions, droplet number and CCN concentration, cloud fraction and droplet number, cloud optical depth and droplet number, and cloud radiative forcing and cloud optical depth. The relationship between cloud optical depth and droplet number can be further decomposed into the sum of two terms involving the relationship of droplet effective radius and cloud liquid water path with droplet number. These relationships can be constrained using observations of recent spatial and temporal variability of these quantities. However, we are most interested in the radiative forcing since the preindustrial era. Because few relevant measurements are available from that era, relationships from recent variability have been assumed to be applicable to the preindustrial to present-day change. Our analysis of Aerosol Comparisons between Observations and Models (AeroCom) model simulations suggests that estimates of relationships from recent variability are poor constraints on relationships from anthropogenic change for some terms, with even the sign of some relationships differing in many regions. Proxies connecting recent spatial/temporal variability to anthropogenic change, or sustained measurements in regions where emissions have changed, are needed to constrain estimates of anthropogenic aerosol impacts on cloud radiative forcing.
14th congress of combustion by-products and their health effects—origin, fate, and health effects of combustion-related air pollutants in the coming era of bio-based energy sources
| Environ Sci Pollut Res
Products of incomplete combustion
The 14th International Congress on Combustion By-Products and Their Health Effects was held in Umeå, Sweden from June 14th to 17th, 2015. The Congress, mainly sponsored by the National Institute of Environmental Health Sciences Superfund Research Program and the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning, focused on the “Origin, fate and health effects of combustion-related air pollutants in the coming era of bio-based energy sources”. The international delegates included academic and government researchers, engineers, scientists, policymakers and representatives of industrial partners. The Congress provided a unique forum for the discussion of scientific advances in this research area since it addressed in combination the health-related issues and the environmental implications of combustion by-products. The scientific outcomes of the Congress included the consensus opinions that: (a) there is a correlation between human exposure to particulate matter and increased cardiac and respiratory morbidity and mortality; (b) because currently available data does not support the assessment of differences in health outcomes between biomass smoke and other particulates in outdoor air, the potential human health and environmental impacts of emerging air-pollution sources must be addressed. Assessment will require the development of new approaches to characterize combustion emissions through advanced sampling and analytical methods. The Congress also concluded the need for better and more sustainable e-waste management and improved policies, usage and disposal methods for materials containing flame retardants.
A Review of More than 20 Years of Aerosol Observation at the High Altitude Research Station Jungfraujoch, Switzerland (3580 m asl)
| Aerosol Air Qual. Res.
Aerosol chemical properties
Aerosol physical properties
Among the worldwide existing long-term aerosol monitoring sites, the Jungfraujoch (JFJ) belongs to the category where both free tropospheric (FT) conditions and influence from planetary boundary layer (PBL) injections can be observed. Thus, it is possible to characterize free tropospheric aerosol as well as the effects of vertical transport of more polluted air from the PBL. This paper summarizes the current knowledge of the key properties for the JFJ aerosol, gained from the large number of in-situ studies from more than 20 years of aerosol measurements at the site. This includes physical, chemical and optical aerosol properties as well as aerosol-cloud interactions and cloud characteristics. It is illustrated that the aerosol size distribution and the aerosol chemical composition are fairly constant in time due to the long distance from aerosol sources, and that many climate relevant aerosol properties can be derived due to this behavior.
XRF measurements of tin, copper and zinc in antifouling paints coated on leisure boats
Tributyltin (TBT) and other organotin compounds have been restricted for use on leisure boats since 1989 in the EU. Nonetheless, release of TBT is observed from leisure boats during hull maintenance work, such as pressure hosing. In this work, we used a handheld X-ray Fluorescence analyser (XRF) calibrated for antifouling paint matrixes to measure tin, copper and zinc in antifouling paints coated on leisure boats in Sweden. Our results show that over 10% of the leisure boats (n = 686) contain >400 μg/cm2 of tin in their antifouling coatings. For comparison, one layer (40 μm dry film) of a TBT-paint equals ≈ 800 μg Sn/cm2. To our knowledge, tin has never been used in other forms than organotin (OT) in antifouling paints. Thus, even though the XRF analysis does not provide any information on the speciation of tin, the high concentrations indicate that these leisure boats still have OT coatings present on their hull. On several leisure boats we performed additional XRF measurements by progressively scraping off the top coatings and analysing each underlying layer. The XRF data show that when tin is detected, it is most likely present in coatings close to the hull with several layers of other coatings on top. Thus, leaching of OT compounds from the hull into the water is presumed to be negligible. The risk for environmental impacts arises during maintenance work such as scraping, blasting and high pressure hosing activities. The data also show that many boat owners apply excessive paint layers when following paint manufacturers recommendations. Moreover, high loads of copper were detected even on boats sailing in freshwater, despite the more than 20 year old ban, which poses an environmental risk that has not been addressed until now.