Permeable reactive barriers (PRBs) remove nitrogen from groundwater by enhancing microbial denitrification. The PRBs consist of woodchips that provide carbon for denitrifiers, but these woodchips also support other anaerobic microbes, including sulfate-reducing bacteria. Some of these anaerobes have the ability to methylate inorganic mercury present in groundwater. Methylmercury is hazardous to human health, so it is essential to understand whether PRBs promote mercury methylation. We examined microbial communities and geochemistry in fresh water and sulfate-enriched PRB flow-through columns by spiking replicates of both treatments with mercuric chloride. We hypothesized that mercury addition could alter bacterial community composition to favor higher abundances of genera containing known methylating taxa and that the sulfate-rich columns would produce more methylmercury after mercury addition, due mainly to an increase in abundance of sulfate reducing bacteria (SRB). However, methylmercury output at the end of the experiment was not different from output at the beginning, due in part to coupled Hg methylation and demethylation. There was a transient reduction in nitrate removal after mercury addition in the sulfate enriched columns, but nitrate removal returned to initial rates after two weeks, demonstrating resilience of the denitrifying community. Since methylmercury output did not increase and nitrate removal was not permanently affected, PRBs could be a low cost approach to combat eutrophication.

Emission of hazardous trace elements (HTEs) from energy production is receiving much attention due to concerns about the toxicity to the ecosystem and human health. This study presented new field measurement data on the HTEs partitioning behavior and size-segregated elemental compositions of gaseous particular matter (PM) generated from a commercial circulating fluidized bed (CFB) power plant. Mineralogical and morphological characteristics of combustion ash and PM2.5 (particle diameter less than 2.5 μm) were determined by X-ray diffractometer (XRD) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS). Functional groups alteration during CFB combustion was characterized by Fourier transform infrared spectroscopy (FTIR). The presence of aliphatic hydrogen at 2910 cm−1 and 2847 cm−1 in the PM2.5 suggested that the aliphatic carbon-rich volatiles were absorbed on the fine particles with large surface area. Fine fly ash (PM2.5) occurred as irregular glass particles or/and as unburned carbon. The typical irregular particles were mainly composed of Al-Si-Ca or Al-Si-Fe phases. The enrichment behavior of HTEs was determined for the airborne size-segregated particular matter. Elemental occurrences, combustion temperature, unburnt carbon, and limestone additives during CFB combustion were critical in the transformation behavior of HTEs. The total potentially mobile pollutants that exit the CFB power plant every year were estimated as follows: 0.22 tons of Cr, 0.12 tons of Co, 0.73 tons of Ni, 0.04 tons of As, 0.07 tons of Se, 3.95 kg of Cd, and 3.34 kg of Sb.

Sewage sludge from a municipal wastewater treatment facility employing activated sludge process was pre-incubated with varying substrates and mixtures of substrates including metformin (MET), guanylurea (GUA) and glucose. The biomass from enriched cultures separately utilising MET and glucose/GUA was then used to investigate the kinetics of aerobic biodegradation of MET and GUA, respectively, as individual substrates in batch reactors. The results showed that GUA can be completely degraded as a nitrogen source when glucose is provided as a carbon and energy source. On the contrary, MET can be biodegraded as a sole carbon and energy source. However, formation of by-product GUA in solution, which acts as a nitrogen source, rapidly increased the degradation rate of MET resembling autocatalytic behaviour. At low starting concentration of 5 mg/L, the specific substrate utilisation rates of MET and GUA were 0.0033 day⁻¹ and 0.0013 day⁻¹, respectively, which is reported first time in this study. Out of the five biodegradation kinetic models used to describe substrate utilisation, the Quiroga-Sales-Romero (QSR) model was found to predict the measured MET and GUA degradation profile well supported by the goodness of fit parameters. Furthermore, the QSR model was able to describe the autocatalytic degradation of MET and the incomplete biodegradation of GUA in solution.

Despite the increase of literature on seabird plastic ingestion in recent years, few studies have assessed how plastic loads vary according to different sampling methods. Most studies use necropsies of seabirds with a natural cause of death, e.g. beached or predated, to determine plastic loads and monitor marine debris. Sampling naturally dead seabirds may be biased as they have perished because of their intrinsic factors, e.g. poor body condition, high parasite loads, sickness or predation, affecting estimates of plastic loads. However, seabirds killed accidentally may be more representative of the population. Here, we used the short-tailed shearwater Ardenna tenuirostris to test different sampling methods: naturally beached fledglings and accidentally road-killed fledglings after being attracted and grounded by artificial lights. We compared plastic load, body condition, and feeding strategies (through using feathers’ δ¹³C and δ¹⁵N isotope niche) between beached and road-killed fledglings. Beached birds showed higher plastic loads, poorer body condition and reduced isotopic variability, suggesting that this group is not a representative subsample of the whole cohort of the fledgling population. Our results might have implications for long-term monitoring programs of seabird plastic ingestion. Monitoring plastic debris through beached birds could overestimate plastic ingestion by the entire population. We encourage the establishment of refined monitoring programs using fledglings grounded by light pollution if available. These samples focus on known cohorts from the same population. The fledgling plastic loads are transferred from parents during parental feeding, accumulating during the chick-rearing period. Thus, these fledglings provide a higher and valuable temporal resolution, which is more useful and informative than unknown life history of beached birds.

Organic tracers are useful for investigating the sources of carbonaceous aerosols but there are still no adequate studies in China. To obtain insights into the diurnal variations, properties, and the influence of regional emission controls on carbonaceous aerosols in Beijing, day-/nighttime PM₂.₅ samples were collected before (Oct. 15th – Nov. 2nd) and during (Nov. 3rd – Nov. 12th) the 2014 Asia-Pacific Economic Cooperation (APEC) summit. Eleven organic compound classes were analysed using gas chromatography/mass spectrometry (GC/MS). In addition, the stable carbon isotope ratios (δ¹³CTC) of total carbon (TC) were detected using an elemental analyser/isotope ratio mass spectrometry (EA/irMS). Most of the organic compounds were more abundant during the night than in the daytime, and their concentrations generally decreased during the APEC. These features were associated with the strict regional emission controls and meteorological conditions. The day/night variations of δ¹³CTC were smaller during the APEC than those before the APEC the summit, suggesting that regionally transported aerosols are potentially played an important role in the loading of organic aerosols in Beijing before the APEC summit. The source apportionment based on the organic tracers suggested that biomass burning, plastic and microbial emissions, and fossil fuel combustion were important sources of organic aerosols in Beijing. Furthermore, a similar contribution of biomass burning to OC before and during the APEC suggests biomass burning was a persistent contributor to PM₂.₅ in Beijing and its surroundings.

Aluminum (Al) phytotoxicity is a major limitation in the production of crops in the soils with pH ≤ 5. Boron (B) is indispensable nutrient for the development of higher plants and B role has been reported in the alleviation Al toxicity. Trifoliate orange rootstock was grown in two B and two Al concentrations. The results of the present study showed that Al toxicity adversely inhibited root elongation and exhibited higher oxidative stress in terms of H2O2 and O2− under B-deficiency. Additionally, the X-ray diffraction (XRD) analysis confirmed the increase of the cellulose crystallinity in the cell wall (CW). Al-induced remarkable variations in the CW components were prominent in terms of alkali-soluble pectin, 2-keto-3-deoxyoctonic acid (KDO) and the degree of methyl-esterification (DME) of pectin. Interesting, B supply reduced the pectin (alkali-soluble) under Al toxicity. Moreover, the results of FTIR (Fourier transform infrared spectroscopy) and 13C-NMR (13C nuclear magnetic resonance) spectra revealed the decrease of carboxyl groups and cellulose by B application during Al exposure. Furthermore, B supply tended to decrease the Al uptake, CW thickness and callose formation. The study concluded that B could mitigate Al phytotoxicity by shielding potential Al binding sites and by reducing Al induced alterations in the CW cellulose and pectin components.

To explore the effect of elevated CO₂ concentrations ([CO₂]) on phosphine formation in paddy fields, the matrix-bound phosphine (MBP) content, different phosphorus fractions and various carbon forms in soil samples from rice cultivation under varying CO₂ concentrations of 400 ppm, 550 ppm and 700 ppm by indoor simulation experiment were determined. This study showed that MBP concentration did not increase significantly with elevated [CO₂] over four-week cultivation periods of rice seedlings, regardless of soil layers. MBP had a significant positive correlation with total phosphorus (TP) and inorganic phosphorus (IP), and multiple stepwise linear regression analysis further indicated that MBP preservation in neutral paddy soils with depths of 0–20 cm may have been due to conversion from FeP and CaP. Based on redundancy analysis and forward selection analysis, speculated that the formation of MBP in the neutral paddy soils as the response to atmospheric elevated [CO₂] was due to two processes: (i) FeP transformation affected by the changes of soil respiration (SCO₂) and TOC was the main precursor for the production of MBP; and (ii) CaP transformation resulting from variation in HCO₃⁻ was the secondary MBP source. The complex combination of these two processes is simultaneously controlled by SCO₂. In a word, the soil environment in the condition of elevated [CO₂] was in favor of MBP storage in neutral paddy soils. The results of our study imply that atmospheric CO₂ participates in and has a certain impact on the global biogeochemical cycle of phosphorus.

Mercury (Hg) and lead (Pb) are widespread contaminants that pose risks to avian scavengers. In fact, Pb exposure is the primary factor limiting population recovery in the endangered California condor (Gymnogyps californianus) and Hg can impair avian reproduction at environmentally relevant exposures. The Pacific Northwest region of the US was historically part of the condor's native range, and efforts are underway to expand recovery into this area. To identify potential threats to reintroduced condors we assessed foraging habitats, Hg and Pb exposure, and physiological responses in two surrogate avian scavenger species (common ravens [Corvus corax] and turkey vultures [Cathartes aura] across the region between 2012 and 2016. Mercury exposure near the Pacific coast was 17–27-fold higher than in inland areas, and stable carbon and sulfur isotopes ratios indicated that coastal scavengers were highly reliant on marine prey. In contrast, Pb concentrations were uniformly elevated across the region, with 18% of the birds exposed to subclinical poisoning levels. Elevated Pb concentrations were associated with lower delta-aminolevulinic acid dehydratase (δ-ALAD) activity, and in ravens there was an interactive effect between Hg and Pb on fecal corticosterone concentrations. This interaction indicated that the effects of Hg and Pb exposure on the stress axis are bidirectional, and depend on the magnitude of simultaneous exposure to the other contaminant. Our results suggest that condors released to the Pacific Northwest may be exposed to both elevated Hg and Pb, posing challenges to management of future condor populations in the Pacific Northwest. Developing a robust monitoring program for reintroduced condors and surrogate scavengers will help both better understand the drivers of exposure and predict the likelihood of impaired health. These findings provide a strong foundation for such an effort, providing resource managers with valuable information to help mitigate potential risks.

Bromoxynil is a widely used nitrile herbicide applied to maize and other cereals in many countries. To date, still little is known about bromoxynil turnover and the structural identity of bromoxynil non-extractable residues (NER) which are reported to occur in high amounts. Therefore, we investigated the microbial turnover of ¹³C-labeled bromoxynil for 32 days. A focus was laid on the estimation of biogenic NER based on the turnover of ¹³C into amino acids (AA). At the end, 25% of ¹³C₆-bromoxynil equivalents were mineralized, 2% assigned to extractable residues and 72.5% to NER. Based on 12% in the ¹³C-total AA and an assumed share of AA of 50% in microbial biomass we arrived at 24% of total ¹³C-biogenic NER. About 33% of the total ¹³C-NER could thus be explained by ¹³C-biogenic NER; 67% was unknown and by definition xenobiotic NER with potential for toxicity. The ¹³C label from ¹³C₆-bromoxynil was mainly detected in the humic acids (28.5%), but significant amounts were also found in non-humics (17.6%), fulvic acids (13.2%) and humins (12.7%). The ¹³C-total amino acids hydrolyzed from humic acids, humins and fulvic acids amounted to 5.2%, 6.1% and 1.2% of ¹³C₆-bromoxynil equivalents, respectively, corresponding to total ¹³C-biogenic NER amounts of 10.4%, 12.2% and 2.4%. The humins contained mostly ¹³C-biogenic NER, whereas the humic and fulvic acids may be dominated by the xenobiotic NER. Due to the high proportion of unknown ¹³C-NER and particularly in the humic and fulvic acids, future studies should focus on the detailed characterization of these fractions.

Recent studies have indicated that urban streets can be hotspots for emissions of methane (CH4) from leaky natural gas lines, particularly in cities with older natural gas distribution systems. The objective of the current study was to determine whether leaking sewer pipes could also be a source of street-level CH4 as well as nitrous oxide (N2O) in Cincinnati, Ohio, a city with a relatively new gas pipeline network. To do this, we measured the carbon (δ13C) and hydrogen (δ2H) stable isotopic composition of CH4 to distinguish between biogenic CH4 from sewer gas and thermogenic CH4 from leaking natural gas pipelines and measured CH4 and N2O flux rates and concentrations at sites from a previous study of street-level CH4 enhancements (77 out of 104 sites) as well as additional sites found through surveying sewer grates and utility manholes (27 out of 104 sites). The average isotopic signatures for δ13C-CH4 and δ2H-CH4 were −48.5‰ ± 6.0‰ and −302‰ ± 142‰. The measured flux rates ranged from 0.0 to 282.5 mg CH4 day−1 and 0.0–14.1 mg N2O day−1 (n = 43). The average CH4 and N2O concentrations measured in our study were 4.0 ± 7.6 ppm and 392 ± 158 ppb, respectively (n = 104). 72% of sites where fluxes were measured were a source of biogenic CH4. Overall, 47% of the sampled sites had biogenic CH4, while only 13% of our sites had solely thermogenic CH4. The other sites were either a source of both biogenic and thermogenic CH4 (13%), and a relatively large portion of sites had an unresolved source (29%). Overall, this survey of emissions across a large urban area indicates that production and emission of biogenic CH4 and N2O is considerable, although CH4 fluxes are lower than those reported for cities with leaky natural gas distribution systems.