Ethylbenzene and toluene degradation under nitrate-, Mn(IV)-, or Fe(III)-reducing conditions was investigated by compound specific stable isotope analysis (CSIA) using three model cultures (Aromatoleum aromaticum EbN1, Georgfuchsia toluolica G5G6, and a Azoarcus-dominated mixed culture). Systematically lower isotope enrichment factors for carbon and hydrogen were observed for particulate Mn(IV). The increasing diffusion distances of toluene or ethylbenzene to the solid Mn(IV) most likely caused limited bioavailability and hence resulted in the observed masking effect. The data suggests further ethylbenzene hydroxylation by ethylbenzene dehydrogenase (EBDH) and toluene activation by benzylsuccinate synthase (BSS) as initial activation steps. Notably, significantly different values in dual isotope analysis were detected for toluene degradation by G. toluolica under the three studied redox conditions, suggesting variations in the enzymatic transition state depending on the available TEA. The results indicate that two-dimensional CSIA has significant potential to assess anaerobic biodegradation of ethylbenzene and toluene at contaminated sites.

Sand beaches are highly dynamic habitats that can experience considerable impacts from oil spills. This review provides a synthesis of the scientific literature on major oil spills and their impacts on sand beaches, with emphasis on studies documenting effects and recoveries of intertidal invertebrate communities. One of the key observations arising from this review is that more attention has generally been given to studying the impacts of oil spills on invertebrates (mostly macrobenthos), and not to documenting their biological recovery. Biological recovery of sand beach invertebrates is highly dynamic, depending on several factors including site-specific physical properties and processes (e.g., sand grain size, beach exposure), the degree of oiling, depth of oil burial, and biological factors (e.g., species-specific life-history traits). Recovery of affected communities ranges from several weeks to several years, with longer recoveries generally associated with physical factors that facilitate oil persistence, or when cleanup activities are absent on heavily oiled beaches. There are considerable challenges in quantifying impacts from spills on sand beach invertebrates because of insufficient baseline information (e.g., distribution, abundance and composition), knowledge gaps in their natural variability (spatial and temporal), and inadequate sampling and replication during and after oil spills. Thus, environment assessments of impacts and recovery require a rigorous experimental design that controls for confounding sources of variability. General recommendations on sampling strategies and toxicity testing, and a preliminary framework for incorporating species-specific life history traits into future assessments are also provided.

Among other climate changes in the southern Baltic, there is a tendency towards warming, especially in autumn-winter. As a result, the ice cover on the coastal zone often fails to occur. This is conducive to the thriving of phytoplankton, in which metals, including mercury, can be accumulated. The dry deposition of atmospheric Hg during heating seasons is more intense than in non-heating seasons, owing to the combustion of fossil fuels for heating purposes. This has resulted in studies into the role of phytoplankton in the introduction of Hg into the first link of trophic chain, as a function of autumn and winter warming in the coastal zone of the lagoon. The studies were conducted at two stations in the coastal zone of the southern Baltic, in the Puck Lagoon, between December 2011 and May 2013. The obtained results show that, in the estuary region, the lack of ice cover can lead to a 30% increase and during an “extremely warm” autumn and winter an increase of up to three-fold in the mean annual Hg pool in phytoplankton (mass of Hg in phytoplankton per liter of seawater). The Hg content in phytoplankton was higher when Mesodinium rubrum was prevalent in the biomass, while the proportion of dinoflagellates was small.

We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L−1) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L−1) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L−1) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

Severe trace metal pollution due to industrial effluents releases was found in Jiulong River Estuary, Southern China. In this study, water samples were collected during effluent release events to study the dynamic changes of environmental conditions and metal partitioning among dissolved, particulate and colloidal phases controlled by estuarine mixing. Intermittent effluent discharges during low tide caused decreasing pH and dissolved oxygen, and induced numerous suspended particulate materials and dissolved organic carbon to the estuary. Different behaviors of Cu, Zn, Ni, Cr and Pb in the dissolved fraction against the conservative index salinity indicated different sources, e.g., dissolved Ni from the intermittent effluent. Although total metal concentrations increased markedly following effluent discharges, Cu, Zn, Cr, Pb were predominated by the particulate fraction. Enhanced adsorption onto particulates in the mixing process resulted in elevated partitioning coefficient (Kd) values for Cu and Zn, and the particle concentration effect was not obvious under such anthropogenic impacts. Colloidal proportion of these metals (especially Cu and Zn) showed positive correlations with dissolved or colloidal organic carbon, suggesting the metal-organic complexation. However, the calculated colloidal partitioning coefficients were relatively constant, indicating the excess binding capacity. Overall, the intermittent effluent discharge altered the particulate/dissolved and colloidal/soluble phase partitioning process and may further influence the bioavailability and potential toxicity to aquatic organisms.

In 2010, an estimate 4.1 million barrels of oil were accidentally released into the Gulf of Mexico (GoM) during the Deepwater Horizon (DWH) Oil Spill. One and a half years after this incident, a set of subtidal and intertidal marsh sediment cores were collected from five stations in Barataria Bay, Louisiana, USA, and analyzed to determine the spatial and vertical distributions and source of hydrocarbon residues based on their chemical composition. An archived core, collected before the DWH oil spill from the same area, was also analyzed to assess the pre-spill hydrocarbon distribution in the area. Analyses of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs) and stable carbon isotope showed that the distribution of petroleum hydrocarbons in Barataria Bay was patchy and limited in areal extent. Significant TPH and ΣPAH concentrations (77,399 μg/g and 219,065 ng/g, respectively) were detected in the surface sediments of one core (i.e., core A) to a depth of 9 cm. Based on a sedimentation rate of 0.39 cm yr−1, determined using 137Cs, the presence of anthropogenic hydrocarbons in these sediment core deposited ca. 50 to 60 years ago. The historical background hydrocarbon concentrations increased significantly at the sediment surface and can be attributed to recent inputs. Although the oil present in the bay's sediments has undergone moderate weathering, biomarker analyses performed on core A samples likely indicated the presence of hydrocarbons from the DWH oil spill. The effects of oiling events on Barataria Bay and other marsh ecosystems in this region remain uncertain, as oil undergoes weathering changes over time.

Understanding the mechanisms of ¹³⁷Cs movement across different ecosystems is crucial for projecting the environmental impact and management of nuclear contamination events. Here, we report differential movement of ¹³⁷Cs in adjacent forest and stream ecosystems. The food webs of the forest and stream ecosystems in our study were similar, in that they were both dominated by detrital-based food webs and the basal energy source was terrestrial litter. However, the concentration of ¹³⁷Cs in stream litter was significantly lower than in forest litter, the result of ¹³⁷Cs leaching from litter in stream water. The difference in ¹³⁷Cs concentrations between the two types of litter was reflected in the ¹³⁷Cs concentrations in the animal community. While the importance of ¹³⁷Cs fallout and the associated transfer to food webs has been well studied, research has been primarily limited to cases in a single ecosystem. Our results indicate that there are differences in the flow of ¹³⁷Cs through terrestrial and aquatic ecosystems, and that ¹³⁷Cs concentrations are reduced in both basal food resources and higher trophic animals in aquatic systems, where primary production is subsidized by a neighboring terrestrial ecosystem.

Fungicides in aquatic environments can impact non-target bacterial and fungal communities and the invertebrate detritivores responsible for the decomposition of allochthonous organic matter. Additionally, in some aquatic systems daily water temperature fluctuations may influence these processes and alter contaminant toxicity, but such temperature fluctuations are rarely examined in conjunction with contaminants. In this study, the shredding amphipod Hyalella azteca was exposed to the fungicide pyraclostrobin in three experiments. Endpoints included mortality, organism growth, and leaf processing. One experiment was conducted at a constant temperature (23 °C), a fluctuating temperature regime (18–25 °C) based on field-collected data from the S. Llano River, Texas, or an adjusted fluctuating temperature regime (20–26 °C) based on possible climate change predictions. Pyraclostrobin significantly reduced leaf shredding and increased H. azteca mortality at concentrations of 40 μg/L or greater at a constant 23 °C and decreased leaf shredding at concentrations of 15 μg/L or greater in the fluctuating temperatures. There was a significant interaction between temperature treatment and pyraclostrobin concentration on H. azteca mortality, body length, and dry mass under direct aqueous exposure conditions. In an indirect exposure scenario in which only leaf material was exposed to pyraclostrobin, H. azteca did not preferentially feed on or avoid treated leaf disks compared to controls. This study describes the influence of realistic temperature variation on fungicide toxicity to shredding invertebrates, which is important for understanding how future alterations in daily temperature regimes due to climate change may influence the assessment of ecological risk of contaminants in aquatic ecosystems.

Transport of environmental pollutants through porous media is influenced by colloids. Co-transport of As(V) and soil colloids at different pH were systematically investigated by monitoring breakthrough curves (BTCs) in saturated sand columns. A solute transport model was applied to characterize transport and retention sites of As(V) in saturated sand in the presence of soil colloids. A colloid transport model and the DLVO theory were used to reveal the mechanism and hypothesis of soil colloid-promoted As(V) transport in the columns. Results showed that rapid transport of soil colloids, regulated by pH and ionic strength, promoted As(V) transport by blocking As(V) adsorption onto sand, although soil colloids had low adsorption for As(V). The promoted transport was more significant at higher concentrations of soil colloids (between 25 mg L−1 and 150 mg L−1) due to greater blocking effect on As(V) adsorption onto the sand surfaces. The blocking effect of colloids was explained by the decreases in both instantaneous (equilibrium) As adsorption and first-order kinetic As adsorption on the sand surface sites. The discovery of this blocking effect improves our understanding of colloid-promoted As transport in saturated porous media, which provides new insights into role of colloids, especially colloids with low As adsorption capacity, in As transport and mobilization in soil-groundwater systems.

Thallium (Tl) is a toxic and non-essential heavy metal. Raw Pb–Zn ores and solid smelting wastes from a large Pb–Zn smelting plant – a typical thallium (Tl) pollution source in South China, were investigated in terms of Tl distribution and fractionation. A modified IRMM (Institute for Reference Materials and Measurement, Europe) sequential extraction scheme was applied on the samples, in order to uncover the geochemical behavior and transformation of Tl during Pb–Zn smelting and to assess the potential environmental risk of Tl arising from this plant. Results showed that the Pb–Zn ore materials were relatively enriched with Tl (15.1–87.7 mg kg−1), while even higher accumulation existed in the electrostatic dust (3280–4050 mg kg−1) and acidic waste (13,300 mg kg−1). A comparison of Tl concentration and fraction distribution in different samples clearly demonstrated the significant role of the ore roasting in Tl transformation and mobilization, probably as a result of alteration/decomposition of related minerals followed by Tl release and subsequent deposition/co-precipitation on fine surface particles of the electrostatic dust and acidic waste. While only 10–30% of total Tl amounts was associated with the exchangeable/acid-extractable fraction of the Pb–Zn ore materials, up to 90% of total Tl was found in this fraction of the electrostatic dust and acidic waste. Taking into account the mobility and bioavailability of this fraction, these waste forms may pose significant environmental risk.