Undissolved humic acid (HA) is known to substantially effect the migration and transformation of hexavalent chromium [Cr(VI)] in soils. The mechanisms of Cr(VI) retention in soils by undissolved HA have been reported; however, past studies are inconclusive about the types of HA functional groups that are involved in Cr(VI) retention and the retention mechanisms. Utilizing a two-dimensional correlation spectroscopy (2DCOS) analysis for FTIR and 13C CP/MAS NMR, this study investigated the variations of HA function groups and molecular structures after reactions with aqueous Cr(VI) under different pH conditions. Based on the changing sequence of functional groups interpreted from the 2DCOS results, a four-step mechanism for Cr(VI) retention was determined as follows: (1) electrostatic adsorption of Cr(VI) to HA surface, (2) complexation of adsorbed Cr(VI) by carboxyl and ester, (3) reduction of complexed Cr(VI) to Cr(III) by phenol and polysaccharide, and (4) complexation of reduced Cr(III) by carboxylic groups. These functional groups that are involved in Cr(VI) retention were determined to occur in aromatic domains.

The toxicity of oil sands process-affected water (OSPW) has been primarily attributed to polar organic constituents, including naphthenic acid fraction components (NAFCs). Our objective was to assess the toxicity of NAFCs derived from fresh and aged OSPW, as well as commercial naphthenic acid (NA) mixtures. Exposures were conducted with three aquatic species: Hyalella azteca (freshwater amphipod), Vibrio fischeri (marine bacterium, Microtox® assay), and Lampsilis cardium (freshwater mussel larvae (glochidia)). Commercial NAs were more toxic than NAFCs, with differences of up to 30-, 4-, and 120-fold for H. azteca, V. fischeri, and L. cardium, respectively, demonstrating that commercial NAs are not reliable surrogates for assessing the toxicity of NAFCs. Differences in toxicity between species were striking for both commercial NAs and NAFCs. Overall, V. fischeri was the least sensitive and H. azteca was the most sensitive organism. Responses of V. fischeri and H. azteca to NAFC exposures were consistent (< 2-fold difference) regardless of source and age of OSPW; however, effects on L. cardium ranged 17-fold between NAFCs. NAFCs derived from fresh OSPW sources were similarly or less toxic to those from aged OSPW. Our results support the need to better characterize the complex mixtures associated with bitumen-influenced waters, both chemically and toxicologically.

Wet deposition is one of the most important and efficient removal mechanisms in the reduction of air pollution. As a key parameter determining wet deposition, the wet scavenging coefficient (WSC) is widely used in chemical transport models (CTMs) and reported values have large uncertainties. In this study, a high-resolution observational dataset of the soluble inorganic aerosols (SO42−, NO3− and NH4+, hereafter SNA) in the air and in rainwater during multiple precipitation events was collected using sequential sampling and used to estimate the below-cloud WSC in Beijing during the summer of 2014. The average concentrations of SNA in precipitation during the observational period were 7.9 mg/L, 6.2 mg/L and 4.6 mg/L, with the contributions from below-cloud scavenging constituting 56%, 61% and 47% of this, respectively. The scavenging ratios of SNA (i.e., the ratio of the concentrations in rain to concentrations in the air) were used with the height of the cloud base and the precipitation intensity to estimate the WSC. The estimated WSC of SO42− is comparable to that reported elsewhere. The relationship between the below-cloud WSC and the precipitation intensity followed an exponential power distribution (K=aPb) for SNA. In contrast to previous studies, this study considers the differences between the chemical compositions of the SNA, with the highest WSC for NO3−, followed by those of SO42− and NH4+. Therefore, we recommend that CTMs include ion specific WSCs in the future.

Nitrated phenols are among the major constituents of brown carbon and affect both climates and ecosystems. However, emissions from biomass burning, which comprise one of the most important primary sources of atmospheric nitrated phenols, are not well understood. In this study, the concentrations and proportions of 10 nitrated phenols, including nitrophenols, nitrocatechols, nitrosalicylic acids, and dinitrophenol, in fine particles from biomass smoke were determined under three different burning conditions (flaming, weakly flaming, and smoldering) with five common types of biomass (leaves, branches, corncob, corn stalk, and wheat straw). The total abundances of fine nitrated phenols produced by biomass burning ranged from 2.0 to 99.5 μg m−3. The compositions of nitrated phenols varied with biomass types and burning conditions. 4-nitrocatechol and methyl nitrocatechols were generally most abundant, accounting for up to 88–95% of total nitrated phenols in flaming burning condition. The emission ratios of nitrated phenols to PM2.5 increased with the completeness of combustion and ranged from 7 to 45 ppmm and from 239 to 1081 ppmm for smoldering and flaming burning, respectively. The ratios of fine nitrated phenols to organic matter in biomass burning aerosols were comparable to or lower than those in ambient aerosols affected by biomass burning, indicating that secondary formation contributed to ambient levels of fine nitrated phenols. The emission factors of fine nitrated phenols from flaming biomass burning were estimated based on the measured mass fractions and the PM2.5 emission factors from literatures and were approximately 0.75–11.1 mg kg−1. According to calculations based on corn and wheat production in 31 Chinese provinces in 2013, the total estimated emission of fine nitrated phenols from the burning of corncobs, corn stalks, and wheat straw was 670 t. This work highlights the apparent emission of methyl nitrocatechols from biomass burning and provides basic data for modeling studies.

Two stages of selection from a pool of 56 fatty acids analyzed in Helix pomatia yielded a set of 12 biomarker acids undergoing significant changes in contact with three microdoses of toxic substances, i.e. three molluscicides containing metaldehyde, methiocarb, and potassium chloride (PC). The proposed palette of acids, including saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), and polyunsaturated fatty acids (PUFA), determined separately in the foot tissues and hepatopancreas of Gastropoda, can be used in ecotoxicological research as a reliable test of the effect of trace doses of stressors. The final set of the biomarker FA comprised C16:0; C18:0; C23:0; C18:1 n-9; C20:1 n-9; C18:2 n-6; C18:3 n-3; C20:2; C20:4 n-6; C20:5 n-3; C22:4 n-6; and C22:5 n-3. A clear physiological response manifested as changes in the content of fatty acids (FA) was observed in the snails even in the case of the lowest doses of the pollutants. All experimental factors analyzed, i.e., the dose (5, 10, or 15 μl 0.01% w/v concentration) and the type of preparation (metaldehyde, methiocarb or PC), had a significant (p ≤ 0.01) impact on the FA composition of the foot and hepatopancreas. Limitation of the analysis to a narrow pool of reactive FA meets the requirements of parameters of biomarkers of exposure and facilitates and accelerates visualization of the bioindicator organism's response to the presence of the stressor in the environment.

The current debate on climate change is over whether global warming can be limited in order to lessen its impacts. In this sense, evidence of a decrease in the statistical polarization in greenhouse gas (GHG) emissions could encourage countries to establish a stronger multilateral climate change agreement. Based on the interregional and intraregional components of the multivariate generalised entropy measures (Maasoumi, 1986), Gigliarano and Mosler (2009) proposed to study the statistical polarization concept from a multivariate view. In this paper, we apply this approach to study the evolution of such phenomenon in the global distribution of the main GHGs. The empirical analysis has been carried out for the time period 1990–2011, considering an endogenous grouping of countries (Aghevli and Mehran, 1981; Davies and Shorrocks, 1989). Most of the statistical polarization indices showed a slightly increasing pattern that was similar regardless of the number of groups considered. Finally, some policy implications are commented.

Levels of neurotoxic methylmercury (MeHg) in phytoplankton are strongly associated to water MeHg concentrations. Because uptake by phytoplankton is the first and largest step of bioaccumulation in aquatic food webs many studies have investigated factors controlling seasonal changes in water MeHg concentrations. However organic matter (OM), widely accepted as an important driver of MeHg production and uptake by phytoplankton, is known for strong interannual variability in concentrations and composition within systems. In this study, we explore the role of OM on spatial and interannual variability of MeHg in a subarctic coastal sea, the northern Baltic Sea. Using MeHg (2014: 80 ± 25 fM; 2015: <LOD fM; 2016: 21 ± 9 fM) and OM measurements during late summer/early fall, we find that dissolved organic carbon (DOC) and humic matter content explain 60% of MeHg variability. We find that while labile DOC increases MeHg levels in the water, humic content reduces it. We propose that the positive association between MeHg and labile DOC shows that labile DOC is a proxy for OM remineralization rate in nearshore and offshore waters. This is consistent with other studies finding that in situ MeHg production in the water column occurs during OM remineralization. The negative association between water humic content and MeHg concentration is most likely due to humic matter decreasing inorganic mercury (HgII) bioavailability to methylating microbes. With these relationships, we develop a statistical model and use it to calculate MeHg concentrations in late summer nearshore and offshore waters between 2006 and 2016 using measured values for water DOC and humic matter content. We find that MeHg concentrations can vary by up to an order of magnitude between years, highlighting the importance of considering interannual variability in water column MeHg concentrations when interpreting both short and long term MeHg trends in biota.

Phytoremediation, a technique used to reclaim heavy metal-contaminated soils, requires an understanding of plant physiological responses to heavy metals. However, the majority of studies documenting heavy metal impact on plant functioning have been performed in laboratory or greenhouse settings. We predicted that increased soil heavy metal concentrations reduce photosynthesis and biomass production in trees growing in metal contaminated soil in a naturally re-vegetated urban brownfield. Leaf gas exchange, leaf carbon and nitrogen concentration, and tree biomass were recorded and compared for Populus deltoides and Populus tremuloides growing in an urban brownfield. The CO2 compensation point (CCP) differed significantly between soil metal concentrations and species, with P. deltoides displaying a greater CCP and P. tremuloides displaying a lower CCP as soil metal concentration increased, despite no changes in dark respiration for either species. In terms of biomass, only total branch weight (TBW) and leaf area (LA) differed significantly between soil metal concentrations, though the difference was largely attributable to variation in diameter at breast height (DBH). Furthermore, TBW and LA values for P. deltoides did not decrease with increasing soil metal concentration. Soil metal concentration, thus, had minimal effect on the relationship between tree age and DBH, and no effect on relationships of tree age and height or LA, respectively. Significant differences between soil metal concentrations and species were found for δ15N (isotopic nitrogen ratio) while leaf nitrogen content (% N) also differed significantly between species. Long-term water use efficiency derived from carbon isotope analysis (iWUEisotope) differed significantly between trees grown on different soil metal concentrations and a significant species-metal concentration interaction was detected indicating that the two study species responded differentially to the soil metal concentrations. Specifically, P. tremuloides enhanced while P. deltoides reduced long-term iWUEisotope as soil metal concentration increased, further emphasizing the importance of species and possible genotype selection for phytoremediation.

In this study, ZnAlTi layered double hydroxide (ZnAlTi-LDH) combined with fullerene (C60) was fabricated by the urea method, and calcined under vacuum atmosphere to obtain nanocomposites of C60-modified ZnAlTi layered double oxide (ZnAlTi-LDO). The morphology, structure and composition of the nanocomposites were analyzed by Scanning Electron Microscopy, High-resolution transmission electron microscopy, X-ray diffraction patterns, Fourier transform infrared and specific surface area. The UV-vis diffuse reflectance spectra indicated that the incorporation of C60 expanded the absorption of ZnAlTi-LDO to visible-light region. The photo-degradation experiment was conducted by using a series of C60 modified ZnAlTi-LDO with different C60 weight percentage to degrade Bisphenol A (BPA) under simulated visible light irradiation. In this experiment, the degradation rate of C60 modified ZnAlTi-LDO in photo-degradation of BPA under simulated visible light irradiation was over 80%. The intermediates formed in the degradation of BPA process by using LDO/C60-5% were 4-hydroxyphenyl-2-propanol, 4-isopropenylphenol and Phenol. Photogenerated holes, superoxide radical species, ·OH and singlet oxygen were considered to be responsible for the photodegradation process, among which superoxide radical species and ·OH played a predominant role in the photocatalytic reaction system. C60 modified ZnAlTi-LDO catalysts for photocatalytic reduction shows great potential in degradation of organic pollutants and environmental remediation.