A synthesis of mercury research in the Southern Hemisphere, part 2: Anthropogenic perturbations.

Environmental mercury (Hg) contamination is a global concern requiring action at national scales. Scientific understanding and regulatory policies are underpinned by global extrapolation of Northern Hemisphere Hg data, despite historical, political, and socioeconomic differences between the hemispheres that impact Hg sources and sinks. In this paper, we explore the primary anthropogenic perturbations to Hg emission and mobilization processes that differ between hemispheres and synthesize current understanding of the implications for Hg cycling. In the Southern Hemisphere (SH), lower historical production of Hg and other metals implies lower present-day legacy emissions, but the extent of the difference remains uncertain. More use of fire and higher deforestation rates drive re-mobilization of terrestrial Hg, while also removing vegetation that would otherwise provide a sink for atmospheric Hg. Prevalent Hg use in artisanal and small-scale gold mining is a dominant source of Hg inputs to the environment in tropical regions. Meanwhile, coal-fired power stations continue to be a significant Hg emission source and industrial production of non-ferrous metals is a large and growing contributor. Major uncertainties remain, hindering scientific understanding and effective policy formulation, and we argue for an urgent need to prioritize research activities in under-sampled regions of the SH.

Emissions and Marine Boundary Layer Concentrations of Unregulated Chlorocarbons Measured at Cape Point, South Africa.

Unregulated chlorocarbons, here defined as dichloromethane (CH2Cl2), perchloroethene (C2Cl4), chloroform (CHCl3), and methyl chloride (CH3Cl), are gases not regulated by the Montreal Protocol. While CH3Cl is the largest contributor of atmospheric chlorine, recent studies have shown that growth in emissions of the less abundant chlorocarbons could pose a significant threat to the recovery of the ozone layer. Despite this, there remain many regions for which no atmospheric monitoring exists, leaving gaps in our understanding of global emissions. Here, we report on a new time series of chlorocarbon measurements from Cape Point, South Africa for 2017, which represent the first published high-frequency measurements of these gases from Africa. For CH2Cl2 and C2Cl4, the majority of mole fraction enhancements were observed from the north, consistent with anthropogenically modified air from Cape Town, while for CHCl3 and CH3Cl, we found evidence for both oceanic and terrestrial sources. Using an inverse method, we estimated emissions for south-western South Africa (SWSA). For each chlorocarbon, SWSA accounted for less than 1% of global emissions. For CH2Cl2 and C2Cl4, we extrapolated using population statistics and found South African emissions of 8.9 (7.4-10.4) Gg yr-1 and 0.80 (0.64-1.04) Gg yr-1, respectively.

Atmospheric HCFC-22, HFC-125, and HFC-152a at Cape Point, South Africa.

One hydrochlorofluorocarbon and two hydrofluorocarbons (HCFC-22, HFC-125, and HFC-152a) were measured in air samples at the Cape Point observatory (CPT), South Africa, during 2017. These data represent the first such atmospheric measurements of these compounds from southwestern South Africa (SWSA). Baseline atmospheric growth rates were estimated to be 8.36, 4.10, and 0.71 ppt year-1 for HCFC-22, HFC-125, and HFC-152a, respectively. The CPT measurements were combined with an inverse model to investigate emissions from SWSA. For all three halocarbons, Cape Town was found to be the dominant source within SWSA. These estimates were extrapolated, based on population statistics, to estimate emissions for the whole of South Africa. We estimate South Africa's 2017 emissions to be 3.0 (1.6-4.4), 0.8 (0.5-1.2), and 1.1 (0.6-1.6) Gg year-1 for HCFC-22, HFC-125, and HFC-152a, respectively. For all three halocarbons, South Africa's contribution to global emissions is small (<2.5%), but future monitoring is needed to ensure South Africa's compliance with regulation set out by the Montreal Protocol and its Amendments.

Methods to Investigate the Global Atmospheric Microbiome.

The interplay between microbes and atmospheric physical and chemical conditions is an open field of research that can only be fully addressed using multidisciplinary approaches. The lack of coordinated efforts to gather data at representative temporal and spatial scales limits aerobiology to help understand large scale patterns of global microbial biodiversity and its causal relationships with the environmental context. This paper presents the sampling strategy and analytical protocols developed in order to integrate different fields of research such as microbiology, -omics biology, atmospheric chemistry, physics and meteorology to characterize atmospheric microbial life. These include control of chemical and microbial contaminations from sampling to analysis and identification of experimental procedures for characterizing airborne microbial biodiversity and its functioning from the atmospheric samples collected at remote sites from low cell density environments. We used high-volume sampling strategy to address both chemical and microbial composition of the atmosphere, because it can help overcome low aerosol and microbial cell concentrations. To account for contaminations, exposed and unexposed control filters were processed along with the samples. We present a method that allows for the extraction of chemical and biological data from the same quartz filters. We tested different sampling times, extraction kits and methods to optimize DNA yield from filters. Based on our results, we recommend supplementary sterilization steps to reduce filter contamination induced by handling and transport. These include manipulation under laminar flow hoods and UV sterilization. In terms of DNA extraction, we recommend a vortex step and a heating step to reduce binding to the quartz fibers of the filters. These steps have led to a 10-fold increase in DNA yield, allowing for downstream omics analysis of air samples. Based on our results, our method can be integrated into pre-existing long-term monitoring field protocols for the atmosphere both in terms of atmospheric chemistry and biology. We recommend using standardized air volumes and to develop standard operating protocols for field users to better control the operational quality.

Atmospheric mercury concentrations observed at ground-based monitoring sites globally distributed in the framework of the GMOS network.

Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010-2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in this paper include a clear gradient of Hg concentrations between the Northern and Southern hemispheres, confirming that the gradient observed is mostly driven by local and regional sources, which can be anthropogenic, natural or a combination of both.

Development of a simplified, cost effective GC-ECD methodology for the sensitive detection of bromoform in the troposphere.

Wherever measurements have been made bromoform was found to be ubiquitous in the surface ocean in pmolar-nmolar concentrations. These measurements show concentrations in coastal regions orders of magnitude higher than in the pelagic oceans. Its atmospheric presence is primarily due to its release from algae and rapid transport to the marine boundary troposphere where it is known to participate in ozone chemistry via photochemical and catalytic pathways. Until quite recently, a limited number of studies existed (compared to other marine volatile organic compounds (VOCs)), mainly due to the analytical challenge(s) presented by the low environmental mixing ratios. In this work we detail the development of a simplified, cost effective method to detect and quantify bromoform in environmental air samples. Air samples (1.5 L) were preconcentrated onto a precooled adsorbent (Carbopack X/Carboxen 1016) trap. These samples were injected by means of rapid thermal desorption for separation and detection by GC-ECD. The system was calibrated by means of a custom-built permeation oven. A linear system response was achieved, having a detection limit of 0.73 ± 0.09 ppt. A range of environmental samples was analysed to demonstrate the ability of the technique to separate and identify bromoform from air samples. The results showed that bromoform concentrations typically averaged 24.7 ± 17.3 ppt in marine air samples, 68.5 ± 26.3 ppt in Cape Town urban air samples and 33.9 ± 40.5 ppt in simulated biomass burning plumes (SBBP).

Saturation of the southern ocean CO2 sink due to recent climate change.

Based on observed atmospheric carbon dioxide (CO2) concentration and an inverse method, we estimate that the Southern Ocean sink of CO2 has weakened between 1981 and 2004 by 0.08 petagrams of carbon per year per decade relative to the trend expected from the large increase in atmospheric CO2. We attribute this weakening to the observed increase in Southern Ocean winds resulting from human activities, which is projected to continue in the future. Consequences include a reduction of the efficiency of the Southern Ocean sink of CO2 in the short term (about 25 years) and possibly a higher level of stabilization of atmospheric CO2 on a multicentury time scale.