The level of phthalate esters (PAEs) alone is not considered to be a sufficient indicator of PAE pollution due to the quick metabolism of PAEs in the biota. The primary metabolites of PAEs, monoalkyl phthalate esters (MPEs), may also be an important indicator. However, PAE metabolism has scarcely been documented in wild marine organisms. We analysed five PAEs [dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), di(2-ethylhexyl) phthalate (DEHP), and di-n-octyl phthalate (DNOP)] and their corresponding MPEs [mono-methyl phthalate (MMP), mono-ethyl phthalate (MEP), mono-n-butyl phthalate (MBP), mono-2-ethylhexyl phthalate (MEHP), and mono-n-octyl phthalate (MNOP)] in 95 wild aquatic marine samples (including fish, prawns and molluscs) collected from the Yangtze River Delta area of the East China Sea. The species-dependent distribution of these compounds was associated with the food habits, living patterns and trophic levels of the biota. Slightly higher levels of hydrophobic PAEs (DBP and DEHP, logKOW 4.27 and 7.33, respectively) were observed in fish species consuming benthic organisms or in demersal fish species, suggesting the importance of benthic organisms and sediment. Trophic dilution of both PAEs and MPEs implies further metabolic transformation at higher trophic levels. MPE tissue distributions in fish demonstrate that the highest concentrations were always observed in bile. Metabolism via the kidney and gill is a probable main way for the relatively less hydrophobic MPEs (logKOW = <4.73, from MMP to MEHP), whereas metabolism via the liver is likely the main way for the most hydrophobic MNOP (logKOW 5.22). Generally, higher detection frequencies of MPEs were observed than those of parent PAEs. Significant liner correlations were observed between the levels of short-branched (carbon atom per chain = <4) MPEs and the sum of PAEs and MPEs (n = 95, p < 0.01), demonstrating that short-branched MPEs can be used as biomarkers of exposure to quantitatively reflect parent PAE contamination in wild marine organisms.

Soils are the largest terrestrial sink for methane (CH4). However, heavy metals may exert toxicity to soil microorganisms, including methanotrophic bacteria. We tested the effect of lead (Pb), zinc (Zn) and nickel (Ni) on CH4 oxidation (1% v/v) and dehydrogenase activity, an index of the activity of the total soil microbial community in Mollic Gleysol soil in oxic and hypoxic conditions (oxia and hypoxia, 20% and 10% v/v O2, respectively). Metals were added in doses corresponding to the amounts permitted of Pb, Zn, Ni in agricultural soils (60, 120, 35 mg kg−1, respectively), and half and double of these doses. Relatively low metal contents and O2 status reflect the conditions of most agricultural soils of temperate regions. Methane consumption showed high tolerance to heavy metals. The effect of O2 status was stronger than that of metals. CH4 consumption was enhanced under hypoxia, where both the start and the completion of the control and contaminated treatment were faster than under oxic conditions. Dehydrogenase activity, showed higher sensitivity to the contamination (except for low Ni dose), with a stronger effect of heavy metals, than that of the O2 status.

Long-lived, upper trophic level marine mammals are vulnerable to bioaccumulation of persistent organic pollutants (POPs). Internal tissues may accumulate and mobilize POP compounds at different rates related to the body condition of the animal and the chemical characteristics of individual POP compounds; however, collection of samples from multiple tissues is a major challenge to ecotoxicology studies of free-ranging marine mammals and the ability to predict POP concentrations in one tissue from another tissue remains rare. Northern elephant seals (Mirounga angustirostris) forage on mesopelagic fish and squid for months at a time in the northeastern Pacific Ocean, interspersed with two periods of fasting on land, which results in dramatic seasonal fluctuations in body condition. Using northern elephant seals, we examined commonly studied tissues in mammalian toxicology to describe relationships and determine predictive equations among tissues for a suite of POP compounds, including ΣDDTs, ΣPCBs, Σchlordanes, and ΣPBDEs. We collected paired blubber (inner and outer) and blood serum samples from adult female and male seals in 2012 and 2013 at Año Nuevo State Reserve (California, USA). For females (N = 24), we sampled the same seals before (late in molting fast) and after (early in breeding fast) their approximately seven month foraging trip. For males, we sampled different seals before (N = 14) and after (N = 15) their approximately four month foraging trip. We observed strong relationships among tissues for many, but not all compounds. Serum POP concentrations were strong predictors of inner blubber POP concentrations for both females and males, while serum was a more consistent predictor of outer blubber for males than females. The ability to estimate POP blubber concentrations from serum, or vice versa, has the potential to enhance toxicological assessment and physiological modeling. Furthermore, predictive equations may illuminate commonalities or distinctions in bioaccumulation across marine mammal species.

Heavy metal(loid) rich ash (≤10,000 mg kg−1 total As, Cr, Cu and Zn) originating from the combustion of contaminated wood was subjected to several experimental procedures involving its incorporation into an upland pasture soil. Ash was added to soil that had been prior amended with local cattle manure, replicating practices employed at the farm scale. Metal(loid) concentrations were measured in soil pore water and ryegrass grown on soil/manure plus ash mixtures (0.1–3.0% vol. ash) in a pot experiment; toxicity evaluation was performed on the same pore water samples by means of a bacterial luminescence biosensor assay. Thereafter a sequential extraction procedure was carried out on selected soil, manure and ash mixtures to elucidate the geochemical association of ash derived metal(loid)s with soil constituents. Predictive modelling was applied to selected data from the pot experiment to determine the risk of transfer of As to meat and milk products in cattle grazing pasture amended with ash.The inclusion of manure to soils receiving ash reduced phyto-toxicity and increased ryegrass biomass yields, compared to soil with ash, but without manure. Elevated As and Cu concentrations in pore water and ryegrass tissue resulting from ash additions were reduced furthest by the inclusion of manure due to an increase in their geochemical association with organic matter. Zinc was the only measured metal(loid) to remain uniformly soluble and bioavailable regardless of the addition of ash and manure. Risk modelling on pot experimental data highlighted that an ash addition of >1% (vol.) to this pasture soil could result in As concentrations in milk and meat products exceeding acceptable limits.The results of this study therefore suggest that even singular low doses of ash applied to soil increase the risk of leaching of metal(loid)s and intensify the risk of As transfer in the food chain.

Microbial degradation of phenol and cresols can occur under oxic and anoxic conditions by different degradation pathways. One recent technique to take insight into reaction mechanisms is compound-specific isotope analysis (CSIA). While enzymes and reaction mechanisms of several degradation pathways have been characterized in (bio)chemical studies, associated isotope fractionation patterns have been rarely reported, possibly due to constraints in current analytical methods. In this study, carbon enrichment factors and apparent kinetic isotope effects (AKIEc) of the initial steps of different aerobic and anaerobic phenol and cresols degradation pathways were analyzed by isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). Significant isotope fractionation was detected for aerobic ring hydroxylation, anoxic side chain hydroxylation, and anoxic fumarate addition, while anoxic carboxylation reactions produced small and inconsistent fractionation. The results suggest that several microbial degradation pathways of phenol and cresols are detectable in the environment by CSIA.

The chemical composition of single particles deposited on industrial filters located in three different chimneys of an iron-manganese (Fe–Mn) alloy manufacturing plant have been compared using aerosol time-of-flight mass spectrometry (ATOFMS) and scanning electron microscopy–energy dispersive X-ray spectrometry (SEM-EDX). Very similar types of particles were observed using both analytical techniques. Calcium-containing particles dominated in the firing area of the sintering unit, Mn and/or Al-bearing particles were observed at the cooling area of the sintering unit, while Mn-containing particles were dominant at the smelting unit. SEM-EDX analysis of particles collected downstream of the industrial filters showed that the composition of the particles emitted from the chimneys is very similar to those collected on the filters. ATOFMS analysis of ore samples was also performed to identify particulate emissions that could be generated by wind erosion and manual activities. Specific particle types have been identified for each emission source (chimneys and ore piles) and can be used as tracers for source apportionment of ambient PM measured in the vicinity of the industrial site.

Production of bisphenol A (BPA) analogues such as bisphenol F (BPF) and bisphenol AF (BPAF) has recently increased, due to clear evidence of adverse effects of BPA on humans and wildlife. Bisphenols (BPs) have already been released into aquatic environment without previous available information about potential adverse effects of BPs and their potential risk to aquatic ecosystems. In this study, lethal and sublethal effects of BPF and BPAF to bacteria, algae, crustacea and fish embryos were investigated and the results were compared to the adverse effects obtained for BPA. We found that BPAF was the most toxic compound to Daphnia magna, Danio rerio and Desmodesmus subspicatus; the lowest 72 h EC50 (median effective concentration) and 21 d NOEC (no observed effect concentration) values were determined at 2.2 mg/L regarding zebrafish hatching success and 0.23 mg/L of BPAF obtained for growth and reproduction of water fleas, respectively. In most cases, BPA was more toxic to D. magna, D. rerio and D. subspicatus in comparison to BPF, but pigmentation of zebrafish embryos after 48 h of exposure and reproduction of water fleas after 21-day D. magna reproductive test exposure to BPF were much more impaired. Risk quotients (measured environmental concentration/21 d NOEC) showed that BPA, BPF and BPAF are recently not chronically hazardous to the survival, reproduction and growth of water fleas in surface waters. On the other hand, we importantly show that currently present BPAF concentrations in surface waters could cause a potential ecological risk to aquatic organisms. In the near future, higher concentrations of BPF and BPAF in surface waters are anticipated and for this reason further testing using test systems with various aquatic species and endpoints are needed to provide additional information about toxic impacts of BPF and BPAF on aquatic biota.

Glomalin-related soil protein (GRSP), which contains glycoproteins produced by arbuscular mycorrhizal fungi (AMF), as well as non-mycorrhizal-related heat-stable proteins, lipids, and humic materials, is generally categorized into two fractions: easily extractable GRSP (EE-GRSP) and total GRSP (T-GRSP). GRSP plays an important role in soil carbon (C) sequestration and can stabilize heavy metals such as lead (Pb), cadmium (Cd), and manganese (Mn). Soil contamination by heavy metals is occurring in conjunction with rising atmospheric CO2 in natural ecosystems due to human activities. However, the response of GRSP to elevated CO2 combined with heavy metal contamination has not been widely reported. Here, we investigated the response of GRSP to elevated CO2 in the rhizosphere of Robinia pseudoacacia L. seedlings in Pb- and Cd-contaminated soils. Elevated CO2 (700 μmol mol−1) significantly increased T- and EE- GRSP concentrations in soils contaminated with Cd, Pb or Cd + Pb. GRSP contributed more carbon to the rhizosphere soil organic carbon pool under elevated CO2 + heavy metals than under ambient CO2. The amount of Cd and Pb bound to GRSP was significantly higher under elevated (compared to ambient) CO2; and elevated CO2 increased the ratio of GRSP-bound Cd and Pb to total Cd and Pb. However, available Cd and Pb in rhizosphere soil under increased elevated CO2 compared to ambient CO2. The combination of both metals and elevated CO2 led to a significant increase in available Pb in rhizosphere soil compared to the Pb treatment alone. In conclusion, increased GRSP produced under elevated CO2 could contribute to sequestration of soil pollutants by adsorption of Cd and Pb.

This study investigates the impact of repeated diesel spills on the structure of intertidal macrofaunal assemblages of a subtropical estuary. Three frequencies of exposure events were compared against two dosages of oil in a factorial experiment with asymmetrical controls. Hypotheses were tested to distinguish between (i) the overall effect of oil spills, (ii) the effect of diesel dosage via different exposure regimes, and (iii) the effect of time since last spill. Repeated oil spills dramatically altered the overall structure of assemblages and reduced the total density of macrofauna and densities of dominant taxa. Increasing the frequency of oil spills negatively affected macrofauna. In general, frequent low-dosage oil spills were more deleterious than infrequent high-dosage ones. However, increases in densities of some taxa, mainly the gastropod Heleobia australis, were observed in response to infrequent spills. Our results highlight the importance of repeated exposure events in determining the extent of oil impacts.

Under the German environmental specimen bank programme bream (Abramis brama) were sampled in six German rivers and analysed for the priority hazardous substances dicofol, hexabromocyclododecane (HBCDD), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD), heptachlor + heptachlor epoxide (HC + HCE), polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxins and -furans and dioxin-like polychlorinated biphenyls (PCDD/Fs + dl-PCBs), and perfluorooctane sulfonic acid (PFOS). The aim was to assess compliance with the EU Water Framework Directive environmental quality standards for biota (EQSBiota) for the year 2013, and to analyse temporal trends for those substances that are of special concern. General compliance was observed for dicofol, HBCDD and HCBD whereas PBDEs exceeded the EQSBiota at all sites. For all other substances compliance in 2013 varied between locations. No assessment was possible for HC + HCE at some sites where the analytical sensitivity was not sufficient to cover the EQSBiota. Trend analysis showed decreasing linear trends for HCB and PFOS at most sampling sites between 1995 and 2014 indicating that the emission reduction measures are effective. Mostly decreasing trends or constant levels were also observed for PCDD/Fs and dl-PCBs. In contrast, increasing trends were detected for PBDEs and HBCDD which were especially pronounced at one Saar site located downstream of the industries and conurbation of Saarbrücken and Völklingen. This finding points to new sources of emissions which should be followed in the coming years.