CHBr3 Emissions Research Articles

Effects of polyethylene microplastics on CHCl3 and CHBr3 fluxes and microbial community in temperate salt marsh soil

Microplastics (MPs) affect the carbon cycle in coastal salt marsh soils. However, studies on their effects on CHCl3 and CHBr3, which are volatile halohydrocarbons that can damage the ozone layer, are lacking. In this study, indoor simulation experiments were conducted to explore the effects of MPs invasion on the source and sink characteristics of soil CHCl3 and CHBr3. The results showed that different concentrations of polyethylene (PE)-MPs promoted CHCl3 and CHBr3 emissions. Emission peaks of the two gases appeared on days 3 and 15 during the culture cycle. CHCl3 and CHBr3 fluxes were mainly affected by soil physicochemical properties and microbial communities. PE-MPs caused changes in soil properties, microorganisms, and related functional genes. Soil total organic carbon, which was significantly and positively correlated with CHCl3. Dissolved organic matter, which was one of the main factors affecting CHBr3, its relative content increased after the addition of PE-MPs. The abundances of Methylocella and Dehalococcoides, which mediate dechlorination reduction, decreased with the addition of PE-MPs. The addition of PE-MPs also significantly varied the abundance of ctrA, which controls dechlorination in soil microorganisms. The gene pceA greatly influenced CHCl3 emissions. In addition, CHBr3 flux was influenced by the interactions between sediment redox and microbial co-metabolic reactions under the control of genes such as TC.FEV.OM and soxB. This study provides theoretical and data support for the source and sink characteristics of volatile halohydrocarbons in coastal salt marshes and highlights the environmental hazards of MPs.

Anthropogenic Bromoform at the Extratropical Tropopause

AbstractBromoform (CHBr3) contributes to stratospheric ozone depletion but is not regulated under the Montreal Protocol due to its short lifetime and large natural sources. Here, we show that anthropogenic sources contribute significantly to the amount of CHBr3 transported into the Northern Hemisphere (NH) extratropical stratosphere. We present a new CHBr3 emission inventory comprised of natural and anthropogenic sources, with the latter estimated from ship ballast, power plant cooling and desalination plant brine water. Including anthropogenic sources in the new inventory increases CHBr3 emissions by up to 31.5% globally and 70.5% in the NH. In consequence, atmospheric CHBr3 is also significantly higher, especially over the NH extratropics during boreal winter. Here anthropogenic sources enhance bromine at the tropopause by 0.9 ppt Br, thus doubling natural CHBr3 abundances. For some latitudes, tropopause bromine increases by 2.4 ppt Br suggesting significant contributions of anthropogenic CHBr3 to the NH lowermost stratosphere.

Potential environmental impact of bromoform from <i>Asparagopsis</i> farming in Australia

Abstract. To mitigate the rumen enteric methane (CH4) produced by ruminant livestock, Asparagopsis taxiformis is proposed as an additive to ruminant feed. During the cultivation of Asparagopsis taxiformis in the sea or in terrestrially based systems, this macroalgae, like most seaweeds and phytoplankton, produces a large amount of bromoform (CHBr3), which contributes to ozone depletion once released into the atmosphere. In this study, we focus on the impact of CHBr3 on the stratospheric ozone layer resulting from potential emissions from proposed Asparagopsis cultivation in Australia. The impact is assessed by weighting the emissions of CHBr3 with its ozone depletion potential (ODP), which is traditionally defined for long-lived halocarbons but has also been applied to very short-lived substances (VSLSs). An annual yield of ∼3.5 × 104 Mg dry weight is required to meet the needs of 50 % of the beef feedlot and dairy cattle in Australia. Our study shows that the intensity and impact of CHBr3 emissions vary, depending on location and cultivation scenarios. Of the proposed locations, tropical farms near the Darwin region are associated with the largest CHBr3 ODP values. However, farming of Asparagopsis using either ocean or terrestrial cultivation systems at any of the proposed locations does not have the potential to significantly impact the ozone layer. Even if all Asparagopsis farming were performed in Darwin, the CHBr3 emitted into the atmosphere would amount to less than 0.02 % of the global ODP-weighted emissions. The impact of remaining farming scenarios is also relatively small even if the intended annual yield in Darwin is scaled by a factor of 30 to meet the global requirements, which will increase the global ODP-weighted emissions up to ∼0.5 %.

Halocarbon emissions by selected tropical seaweeds exposed to different temperatures

Four tropical seaweeds, Gracilaria manilaensis Yamamoto & Trono, Ulva reticulata Forsskål, Kappaphycus alvarezii (Doty) L.M.Liao and Turbinaria conoides (J.Agardh) Kützing, collected from various habitats throughout Malaysia, were subjected to temperatures of 40, 35, 30, 25 and 20 °C in the laboratory. An exposure range of 21–38 °C is reported for Malaysian waters. The effect of the temperature exposures on the halocarbon emissions of the seaweeds were determined 4 and 28 h after treatment. The emission rates for a suite of six halocarbons commonly emitted by seaweeds, bromoform (CHBr3), dibromomethane (CH2Br2), diiodomethane (CH2I2), iodomethane (CH3I), dibromochloromethane (CHBr2Cl) and dichlorobromomethane (CHBrCl2), were measured using a cryogenic purge-and-trap sample preparation system coupled to a gas chromatography–mass spectrometry. The emission rate of CHBr3 was the highest of the six halocarbons for all the seaweeds under all the temperatures tested, followed by CH2Br2, and CH2I2. The emission rates were affected by temperature change and exposure duration, but overall responses were unique to each seaweed species. Larger decreases in the emissions of CHBr3, CH2Br2, CH2I2 and CHBr2Cl were found for K. alvarezii and T. conoides after 4 h at 40 °C. In both cases there was a >90% (p < 0.05) reduction in the Fv/Fm value suggesting that photosynthetic actitivity was severely compromised. After a 28 h exposure period, strong negative correlations (r = −0.69 to −0.95; p < 0.01) were observed between temperature and the emission of CHBr3, CH2Br2 and CH2I2 for U. reticulata, K. alvarezii and T. conoides. This suggests a potential decrease in the halocarbon emissions from these tropical seaweeds, especially where the temperature increase is a prolonged event. Strong correlations were also seen between seaweed chlorophyll and carotenoid pigment contents and the emission rates for CHBr3, CH2Br2 and CH2I2 (r = 0.48 to 0.96 and −0.49 to −0.96; p < 0.05). These results suggest that the regulation of halocarbon production versus reactive oxygen species production in seaweeds is an area worthy of further exploration.

On the emissions and transport of bromoform: sensitivity to model resolution and emission location

Abstract. Bromoform (CHBr3) is a short-lived species with an important but poorly quantified ocean source. It can be transported to the Tropical Tropopause Layer (TTL), in part by rapid, deep convective lifting, from where it can influence the global stratospheric ozone budget. In a modelling study, we investigate the importance of the regional distribution of the emissions and of model resolution for the transport of bromoform to the TTL. We use two idealized CHBr3 emission fields (one coastal, one uniformly distributed across the oceans) implemented in high- and coarse-resolution (HR and CR) versions of the same global model and focus on February as the period of peak convection in the West Pacific. Using outgoing long-wave radiation and precipitation as metrics, the HR version of the model is found to represent convection better. In the more realistic HR model version, the coastal emission scenario leads to 15–20 % more CHBr3 in the global TTL, and up to three times more CHBr3 in the TTL over the Maritime Continent, than when uniform emissions of the same tropical magnitude are employed. Using the uniform emission scenario in both model versions, the distribution of CHBr3 at 15.7 km (approximately the level of zero net radiative heating) is qualitatively consistent with the differing geographic distributions of convection. However, averaged over the whole tropics, the amount of CHBr3 in the TTL in the two model versions is similar. Using the coastal scenario, in which emissions are particularly high in the Maritime Continent because of its long coastlines, the mixing ratio of CHBr3 in the TTL is enhanced over the Maritime Continent in both model versions. The enhancement is larger, and the peak in CHBr3 mixing ratio occurs at a higher altitude, in the HR model version. Our regional-scale results indicate that using aircraft measurements and coarse global models to infer CHBr3 emissions will be very difficult, particularly if (as is possible) emissions are distributed heterogeneously and in regions of strong convective activity. In contrast, the global-scale agreement between our CR and HR calculations suggests model resolution is less vital for studies focused on the transport of bromine into the global stratosphere.

Oceanic bromoform emissions weighted by their ozone depletion potential

Abstract. At present, anthropogenic halogens and oceanic emissions of very short-lived substances (VSLSs) both contribute to the observed stratospheric ozone depletion. Emissions of the long-lived anthropogenic halogens have been reduced and are currently declining, whereas emissions of the biogenic VSLSs are expected to increase in future climate due to anthropogenic activities affecting oceanic production and emissions. Here, we introduce a new approach for assessing the impact of oceanic halocarbons on stratospheric ozone by calculating their ozone depletion potential (ODP)-weighted emissions. Seasonally and spatially dependent, global distributions are derived within a case-study framework for CHBr3 for the period 1999–2006. At present, ODP-weighted emissions of CHBr3 amount up to 50 % of ODP-weighted anthropogenic emissions of CFC-11 and to 9 % of all long-lived ozone depleting halogens. The ODP-weighted emissions are large where strong oceanic emissions coincide with high-reaching convective activity and show pronounced peaks at the Equator and the coasts with largest contributions from the Maritime Continent and western Pacific Ocean. Variations of tropical convective activity lead to seasonal shifts in the spatial distribution of the trajectory-derived ODP with the updraught mass flux, used as a proxy for trajectory-derived ODP, explaining 71 % of the variance of the ODP distribution. Future climate projections based on the RCP 8.5 scenario suggest a 31 % increase of the ODP-weighted CHBr3 emissions by 2100 compared to present values. This increase is related to a larger convective updraught mass flux in the upper troposphere and increasing emissions in a future climate. However, at the same time, it is reduced by less effective bromine-related ozone depletion due to declining stratospheric chlorine concentrations. The comparison of the ODP-weighted emissions of short- and long-lived halocarbons provides a new concept for assessing the overall impact of oceanic halocarbon emissions on stratospheric ozone depletion for current conditions and future projections.

Bromocarbons in the tropical coastal and open ocean atmosphere during the 2009 Prime Expedition Scientific Cruise (PESC-09)

Abstract. Atmospheric concentrations of very short-lived species (VSLS) bromocarbons, including CHBr3, CH2Br2, CHCl2Br, CHClBr2, and CH2BrCl, were measured in the Strait of Malacca and the South China and Sulu–Sulawesi seas during a two-month research cruise in June–July 2009. The highest bromocarbon concentrations were found in the Strait of Malacca, with smaller enhancements in coastal regions of northern Borneo. CHBr3 was the most abundant bromocarbon, ranging from 5.2 pmol mol−1 in the Strait of Malacca to 0.94 pmol mol−1 over the open ocean. Other bromocarbons showed lower concentrations, in the range of 0.8–1.3 pmol mol−1 for CH2Br2, 0.1–0.5 pmol mol−1 for CHCl2Br, and 0.1–0.4 pmol mol−1 for CHClBr2. There was no significant correlation between bromocarbons and in situ chlorophyll a, but positive correlations with both MODIS and SeaWiFS satellite chlorophyll a. Together, the short-lived bromocarbons contribute an average of 8.9 pmol mol−1 (range 5.2–21.4 pmol mol−1) to tropospheric bromine loading, which is similar to that found in previous studies from global sampling networks (Montzka et al., 2011). Statistical tests showed strong Spearman correlations between brominated compounds, suggesting a common source. Log–log plots of CHBr3/CH2Br2 versus CHBr2Cl/CH2Br2 show that both chemical reactions and dilution into the background atmosphere contribute to the composition of these halocarbons at each sampling point. We have used the correlation to make a crude estimate of the regional emissions of CHBr3 and to derive a value of 32 Gg yr−1 for the Southeast (SE) Asian region (10° N–20° S, 90–150° E). Finally, we note that satellite-derived chlorophyll a (chl a) products do not always agree well with in situ measurements, particularly in coastal regions of high turbidity, meaning that satellite chl a may not always be a good proxy for marine productivity.

Estimates of tropical bromoform emissions using an inversion method

Abstract. Bromine plays an important role in ozone chemistry in both the troposphere and stratosphere. When measured by mass, bromoform (CHBr3) is thought to be the largest organic source of bromine to the atmosphere. While seaweed and phytoplankton are known to be dominant sources, the size and the geographical distribution of CHBr3 emissions remains uncertain. Particularly little is known about emissions from the Maritime Continent, which have usually been assumed to be large, and which appear to be especially likely to reach the stratosphere. In this study we aim to reduce this uncertainty by combining the first multi-annual set of CHBr3 measurements from this region, and an inversion process, to investigate systematically the distribution and magnitude of CHBr3 emissions. The novelty of our approach lies in the application of the inversion method to CHBr3. We find that local measurements of a short-lived gas like CHBr3 can be used to constrain emissions from only a relatively small, sub-regional domain. We then obtain detailed estimates of CHBr3 emissions within this area, which appear to be relatively insensitive to the assumptions inherent in the inversion process. We extrapolate this information to produce estimated emissions for the entire tropics (defined as 20° S–20° N) of 225 Gg CHBr3 yr−1. The ocean in the area we base our extrapolations upon is typically somewhat shallower, and more biologically productive, than the tropical average. Despite this, our tropical estimate is lower than most other recent studies, and suggests that CHBr3 emissions in the coastline-rich Maritime Continent may not be stronger than emissions in other parts of the tropics.

Emission of atmospherically significant halocarbons by naturally occurring and farmed tropical macroalgae

Abstract. Current estimates of global halocarbon emissions highlight the tropical coastal environment as an important source of very short-lived (VSL) biogenic halocarbons to the troposphere and stratosphere, due to a combination of assumed high primary productivity in tropical coastal waters and the prevalence of deep convective transport, potentially capable of rapidly lifting surface emissions to the upper troposphere/lower stratosphere. However, despite this perceived importance, direct measurements of tropical coastal biogenic halocarbon emissions, notably from macroalgae (seaweeds), have not been made. In light of this, we provide the first dedicated study of halocarbon production by a range of 15 common tropical macroalgal species and compare these results to those from previous studies of polar and temperate macroalgae. Variation between species was substantial; CHBr3 production rates, measured at the end of a 24 h incubation, varied from 1.4 to 1129 pmol g FW−1 h−1 (FW = fresh weight of sample). We used our laboratory-determined emission rates to estimate emissions of CHBr3 and CH2Br2 (the two dominant VSL precursors of stratospheric bromine) from the coastlines of Malaysia and elsewhere in South East Asia (SEA). We compare these values to previous top-down model estimates of emissions from these regions and, by using several emission scenarios, we calculate an annual CHBr3 emission of 40 (6–224 Mmol Br−1 yr), a value that is lower than previous estimates. The contribution of tropical aquaculture to current emission budgets is also considered. Whilst the current aquaculture contribution to halocarbon emissions in this regional is small, the potential exists for substantial increases in aquaculture to make a significant contribution to regional halocarbon budgets.

Air-sea fluxes of biogenic bromine from the tropical and North Atlantic Ocean

Abstract. Air-sea fluxes and bulk seawater and atmospheric concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) were measured during two research cruises in the northeast Atlantic (53–59° N, June–July 2006) and tropical eastern Atlantic Ocean including over the African coastal upwelling system (16–35° N May–June 2007). Saturations and sea-air fluxes of these compounds generally decreased in the order coastal &gt; upwelling &gt; shelf &gt; open ocean, and outside of coastal regions, a broad trend of elevated surface seawater concentrations with high chlorophyll-a was observed. We show that upwelling regions (coastal and equatorial) represent regional hot spots of bromocarbons, but are probably not of major significance globally, contributing at most a few percent of the total global emissions of CHBr3 and CH2Br2. From limited data from eastern Atlantic coastlines, we tentatively suggest that globally, coastal oceans (depth &lt;180 m) together contribute ~2.5 (1.4–3.5) Gmol Br yr−1 of CHBr3, excluding influences from anthropogenic sources such as coastal power stations. This flux estimate is close to current estimates of the total open ocean source. We also show that the concentration ratio of CH2Br2/CHBr3 in seawater is a strong function of concentration (and location), with a lower CH2Br2/CHBr3 ratio found in coastal regions near to macroalgal sources.

Atmospheric bromoform at Mace Head, Ireland: seasonality and evidence for a peatland source

Abstract. In situ atmospheric observations of bromoform (CHBr3) made over a 2.5 year period at Mace Head, Ireland from May 2001- Dec 2003, including during the NAMBLEX (North Atlantic Marine Boundary Layer Experiment) campaign, show broad maxima from spring until autumn and winter minima, with mixing ratios of 5.3+1.0 pptv (mid March - mid October) and 1.8+0.8 pptv (December-February). This indicates that, unlike CHCl3, which has a summer minimum and winter maximum at Mace Head, local biological sources of CHBr3 have a greater influence on the atmospheric data than photochemical decay during long-range transport. The emission sources are predominantly macroalgal, but we find evidence for a small terrestrial flux from peatland ecosystems, which so far has not been accounted for in the CHBr3 budget. Sharp increases in CHCl3 and CHBr3 concentrations and decreases in O3 concentrations occurred at night when the wind direction switched from an ocean- to a land-based sector (land breeze) and the wind speed dropped to below 5 ms-1. These observations infer a shallow atmospheric boundary layer with increased O3 deposition and concentration of local emissions of both CHCl3 and CHBr3. The ratio of ΔCHCl3/ΔCHBr3 varied strongly according to the prevailing wind direction; from 0.60+0.15 in south-easterly (100-170° and northerly (340-20°) air to 2.5+0.4 in north-easterly (40-70°) air. Of these land-sectors, the south-easterly air masses are likely to be strongly influenced by macroalgal beds along the coast and the emission ratios probably reflect those from seaweeds in addition to land sources. The north-easterly airmasses however had an immediate fetch inland, which locally is comprised of coastal peatland ecosystems (peat bogs and coastal conifer plantations), previously identified as being strong sources of atmospheric CHCl3 under these conditions. Although we cannot entirely rule out other local land or coastal sources, our observations also suggest peatland ecosystem emissions of CHBr3. We use correlations between CHCl3 and CHBr3 during the north-easterly land breeze events in conjunction with previous estimates of local wetland CHCl3 release to tentatively deduce a global wetland CHBr3 source of 20.4(0.4-948) Gg yr-1, which is approximately 7% of the total global source.