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Benzene, toluene, ethylbenzene and xylenes can contribute to hydroxyl reactivity and secondary aerosol formation in the atmosphere. These aromatic hydrocarbons are typically classified as anthropogenic air pollutants, but there is growing evidence of biogenic sources, such as emissions from plants and phytoplankton. Here we use a series of shipborne measurements of the remote marine atmosphere, seawater mesocosm incubation experiments and phytoplankton laboratory cultures to investigate potential marine biogenic sources of these compounds in the oceanic atmosphere. Laboratory culture experiments confirmed marine phytoplankton are a source of benzene, toluene, ethylbenzene, xylenes and in mesocosm experiments their sea-air fluxes varied between seawater samples containing differing phytoplankton communities. These fluxes were of a similar magnitude or greater than the fluxes of dimethyl sulfide, which is considered to be the key reactive organic species in the marine atmosphere. Benzene, toluene, ethylbenzene, xylenes fluxes were observed to increase under elevated headspace ozone concentration in the mesocosm incubation experiments, indicating that phytoplankton produce these compounds in response to oxidative stress. Our findings suggest that biogenic sources of these gases may be sufficiently strong to influence atmospheric chemistry in some remote ocean regions.

Ocean acidification and warming will alter phytoplankton biomass and composition, yet despite numerous studies, there are few consistent responses on which to base predictions. To determine the responses of chlorophyll-a and phytoplankton size and composition to predicted lower pH (−0.33 to −0.5) alone, and also combined with elevated temperature (+2.5–3.5 °C), two mesocosm experiments were carried out in austral spring and autumn in temperate New Zealand coastal waters. Lower pH alone had no effect on chlorophyll-a in either experiment and, as the treatment pH was lower than the pH minimum recorded in a parallel four-year time series, this lack of response in chlorophyll-a was not attributable to prior in situ exposure. Conversely, chlorophyll-a increased under lower pH and warming in both experiments, with the large (>20 µm) phytoplankton size fraction showing opposing responses under nutrient deplete and replete conditions. Diatom biomass also increased in both treatments when nutrient availability was maintained, with a dominant pennate species Cylindrotheca clostridium emerging. The results highlight the value of contextual time series for experimental interpretation, and also the importance of assessing warming and acidification together using regionally representative nutrient concentrations, for prediction of coastal phytoplankton response to climate change.

Cold seeps are areas characterised by specialized biological communities that rely on chemosynthesis for their nutrition. To date, research conducted on New Zealand’s Hikurangi Margin seep communities has focused on communities at 650-1200 m water depth. Here, we characterize the macrofaunal nematode communities of New Zealand cold seeps for the first time, and at deeper (> 1200 m) seep locations (Maungaroa, Glendhu and Urutī South). There were no significant difference in nematode abundance, species richness, diversity and evenness among the seep areas, which may reflect the lack of difference in most sediment variables. However, a consistent spatial pattern in nematode abundance was observed within all the seep areas on the Hikurangi Margin: abundance was highest at or near the seep centre, decreased steeply away from the centre and was low in the periphery. These spatially consistent patterns reflect the influence of methane seepage, which appears limited to the inner 150-200 m radius of each area, on nematode abundance via input of chemosynthetic food sources. We found significant differences in nematode community structure among all three areas, with most of the heterogeneity in community structure between the shallow Urutī South area and deeper Maungaroa and Glendhu areas, and differences among nematode communities of high, medium and low abundance associated with site-specific gradients in methane seepage. Within area variability in nematode community structure was mainly correlated with food availability and sediment grain size. Consistent with previous investigations of seep nematodes, we did not find evidence of seep endemics. Although deposit feeders were generally the most abundant feeding group, there were differences in the relative abundances of different feeding groups such as microvores and epigrowth feeders among the seep areas, and as a function of distance from the centre of the seep areas. Impact on seep communities from gas hydrate extraction processes may occur via reduction or potentially cessation of free-gas methane supply to the seafloor, ‘sand’ production at the seafloor due to the physical degradation of the substrate structure, or alteration of the structural integrity of the seafloor substrate. Any spatial management options considered for managing these impacts should reflect the differences in benthic community structure between depths and locations on the Hikurangi Margin.

The oceanic frontal region above the Chatham Rise east of New Zealand was investigated during the late austral summer season in February and March 2012. Despite its potential importance as a source of marine-originating and climate-relevant compounds, such as dimethyl sulfide (DMS) and its algal precursor dimethylsulfoniopropionate (DMSP), little is known of the processes fuelling the reservoirs of these sulfur (S) compounds in the water masses bordering the subtropical front (STF). This study focused on two opposing short-term fates of DMSP-S following its uptake by microbial organisms (either its conversion into DMS or its assimilation into bacterial biomass) and has not considered dissolved non-volatile degradation products. Sampling took place in three phytoplankton blooms (B1, B2, and B3) with B1 and B3 occurring in relatively nitrate-rich, dinoflagellate-dominated subantarctic waters, and B2 occurring in nitrate-poor subtropical waters dominated by coccolithophores. Concentrations of total DMSP (DMSPt) and DMS were high across the region, up to 160 and 14.5 nmol L−1, respectively. Pools of DMSPt showed a strong association with overall phytoplankton biomass proxied by chlorophyll a (rs  =  0.83) likely because of the persistent dominance of dinoflagellates and coccolithophores, both DMSP-rich taxa. Heterotrophic microbes displayed low S assimilation from DMSP (less than 5 %) likely because their S requirements were fulfilled by high DMSP availability. Rates of bacterial protein synthesis were significantly correlated with concentrations of dissolved DMSP (DMSPd, rs  =  0.86) as well as with the microbial conversion efficiency of DMSPd into DMS (DMS yield, rs  =  0.84). Estimates of the potential contribution of microbially mediated rates of DMS production (0.1–27 nmol L−1 day−1) to the near-surface concentrations of DMS suggest that bacteria alone could not have sustained DMS pools at most stations, indicating an important role for phytoplankton-mediated DMS production. The findings from this study provide crucial information on the distribution and cycling of DMS and DMSP in a critically under-sampled area of the global ocean, and they highlight the importance of oceanic fronts as hotspots of the production of marine biogenic S compounds.

The cycling of the trace gas dimethyl sulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) may be affected by future ocean acidification and warming. DMSP and DMS concentrations were monitored over 20-days in four mesocosm experiments in which the temperature and pH of coastal water were manipulated to projected values for the year 2100 and 2150. This had no effect on DMSP in the two-initial nutrient-depleted experiments; however, in the two nutrient-amended experiments, warmer temperature combined with lower pH had a more significant effect on DMSP & DMS concentrations than lower pH alone. Overall, this indicates that future warming may have greater influence on DMS production than ocean acidification. The observed reduction in DMSP at warmer temperatures was associated with changes in phytoplankton community and in particular with small flagellate biomass. A small decrease in DMS concentration was measured in the treatments relative to other studies, from −2% in the nutrient-amended low pH treatment to −16% in the year 2150 pH and temperature conditions. Temporal variation was also observed with DMS concentration increasing earlier in the higher temperature treatment. Nutrient availability and community composition should be considered in models of future DMS.

The flux of dimethylsulfide (DMS) to the atmosphere is generally inferred using water sampled at or below 2 m depth, thereby excluding any concentration anomalies at the air–sea interface. Two independent techniques were used to assess the potential for near-surface DMS enrichment to influence DMS emissions and also identify the factors influencing enrichment. DMS measurements in productive frontal waters over the Chatham Rise, east of New Zealand, did not identify any significant gradients between 0.01 and 6 m in sub-surface seawater, whereas DMS enrichment in the sea-surface microlayer was variable, with a mean enrichment factor (EF; the concentration ratio between DMS in the sea-surface microlayer and in sub-surface water) of 1.7. Physical and biological factors influenced sea-surface microlayer DMS concentration, with high enrichment (EF > 1.3) only recorded in a dinoflagellate-dominated bloom, and associated with low to medium wind speeds and near-surface temperature gradients. On occasion, high DMS enrichment preceded periods when the air–sea DMS flux, measured by eddy covariance, exceeded the flux calculated using National Oceanic and Atmospheric Administration (NOAA) Coupled-Ocean Atmospheric Response Experiment (COARE) parameterized gas transfer velocities and measured sub-surface seawater DMS concentrations. The results of these two independent approaches suggest that air–sea emissions may be influenced by near-surface DMS production under certain conditions, and highlight the need for further study to constrain the magnitude and mechanisms of DMS production in the sea-surface microlayer.

As the sea surface microlayer (SML) is the uppermost oceanic layer and differs in biogeochemical composition to the underlying subsurface water (SSW), it is important to determine whether processes in the SML modulate gas exchange, particularly for climate active gases. Enrichment of dimethyl sulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) has been reported in the SML, but it remains unclear how this is maintained whilst DMS is lost to the atmosphere. To examine this, a comprehensive study of DMS source and sink processes, including production, consumption, and net response to irradiance, was carried out in deck-board incubations of SML water at five locations in different water masses in the southwestern Pacific east of New Zealand. Net consumption of DMSP and production of DMS in the light and dark occurred at all sites. The net response of DMS and DMSP to irradiance varied between stations but was always lower than conversion of DMSP to DMS in the dark. In addition, DMS photolytic turnover was slower than reported elsewhere, which was unexpected given the high light exposure in the SML incubations. Although no relationships were apparent between DMS process rates and biogeochemical variables, including chlorophyll a, bacteria, and phytoplankton groups, net bacterial DMSP consumption was correlated with DMSP and DMS concentrations and also dinoflagellate and Gymnodinium spp. biomass, supporting the findings of a companion study that dinoflagellates play an important role in DMS cycling in the SML. However, net DMS production rates and accumulation were low relative to regional air–sea DMS loss, indicating that DMS cycling within the SML is unlikely to influence regional DMS emissions.

Estuary ecological resilience can be gauged by response of estuary trophic state to abatement of nutrient pollution. Changes in trophic indicators were studied in the Avon-Heathcote Estuary (AHE) in Christchurch, New Zealand, over 6 years, spanning diversion of city wastewater inputs to an offshore outfall in 2010, and to temporary enrichment caused by the 2011 Christchurch earthquake. It was hypothesised that the tidally well-flushed and sandy AHE would not harbour a ‘legacy’ of eutrophication and would rapidly gain improved ecological function following the diversion. AHE sediments were coarse (156 µm median grain size) with low organic matter (OM 1.2%, N 0.03%, C 0.3%), which changed little either with diversion or earthquake. Upon diversion, median water column and porewater ammonium (36, 185 µmol) decreased by 87% and 57%, respectively, benthic microalgae (269 mg chlorophyll-a m⁻²) fell by 58%, and enrichment-affiliated polychaetes (3700–8000 m⁻²) fell by 60–80% at sites with largest benthic microalgal reductions, all within <1–2 years. Oxygen and ammonium fluxes were usually oligotrophic and changed little upon diversion, except near the historic wastewater discharge site. Denitrification became more important for N loss, increasing from 5 to 29% of estuary N load. Responses to earthquake-driven enrichment were transient. Despite decades of heavy N loading and eutrophic growths of benthic microalgae and macroalgae, the AHE did not store a eutrophic legacy in its sediments. It reacted rapidly to improved water quality allowed by the outfall, showing that this common estuary type (sandy, well-flushed tidal lagoon) was resilient to eutrophication upon stressor removal.

The goal of the Sea2Cloud project is to study the interplay between surface ocean biogeochemical and physical properties, fluxes to the atmosphere, and ultimately their impact on cloud formation under minimal direct anthropogenic influence. Here we present an interdisciplinary approach, combining atmospheric physics and chemistry with marine biogeochemistry, during a voyage between 41° and 47°S in March 2020. In parallel to ambient measurements of atmospheric composition and seawater biogeochemical properties, we describe semicontrolled experiments to characterize nascent sea spray properties and nucleation from gas-phase biogenic emissions. The experimental framework for studying the impact of the predicted evolution of ozone concentration in the Southern Hemisphere is also detailed. After describing the experimental strategy, we present the oceanic and meteorological context including provisional results on atmospheric thermodynamics, composition, and flux measurements. In situ measurements and flux studies were carried out on different biological communities by sampling surface seawater from subantarctic, subtropical, and frontal water masses. Air–Sea-Interface Tanks (ASIT) were used to quantify biogenic emissions of trace gases under realistic environmental conditions, with nucleation observed in association with biogenic seawater emissions. Sea spray continuously generated produced sea spray fluxes of 34% of organic matter by mass, of which 4% particles had fluorescent properties, and which size distribution resembled the one found in clean sectors of the Southern Ocean. The goal of Sea2Cloud is to generate realistic parameterizations of emission flux dependences of trace gases and nucleation precursors, sea spray, cloud condensation nuclei, and ice nuclei using seawater biogeochemistry, for implementation in regional atmospheric models.

Establishing the relationship between marine boundary layer (MBL) aerosols and surface water biogeochemistry is required to understand aerosol and cloud production processes over the remote ocean and represent them more accurately in earth system models and global climate projections. This was addressed by the SOAP (Surface Ocean Aerosol Production) campaign, which examined air–sea interaction over biologically productive frontal waters east of New Zealand. This overview details the objectives, regional context, sampling strategy and provisional findings of a pilot study, PreSOAP, in austral summer 2011 and the following SOAP voyage in late austral summer 2012. Both voyages characterized surface water and MBL composition in three phytoplankton blooms of differing species composition and biogeochemistry, with significant regional correlation observed between chlorophyll a and DMSsw. Surface seawater dimethylsulfide (DMSsw) and associated air–sea DMS flux showed spatial variation during the SOAP voyage, with maxima of 25 nmol L−1 and 100 µmol m−2 d−1, respectively, recorded in a dinoflagellate bloom. Inclusion of SOAP data in a regional DMSsw compilation indicates that the current climatological mean is an underestimate for this region of the southwest Pacific. Estimation of the DMS gas transfer velocity (kDMS) by independent techniques of eddy covariance and gradient flux showed good agreement, although both exhibited periodic deviations from model estimates. Flux anomalies were related to surface warming and sea surface microlayer enrichment and also reflected the heterogeneous distribution of DMSsw and the associated flux footprint. Other aerosol precursors measured included the halides and various volatile organic carbon compounds, with first measurements of the short-lived gases glyoxal and methylglyoxal in pristine Southern Ocean marine air indicating an unidentified local source. The application of a real-time clean sector, contaminant markers and a common aerosol inlet facilitated multi-sensor measurement of uncontaminated air. Aerosol characterization identified variable Aitken mode and consistent submicron-sized accumulation and coarse modes. Submicron aerosol mass was dominated by secondary particles containing ammonium sulfate/bisulfate under light winds, with an increase in sea salt under higher wind speeds. MBL measurements and chamber experiments identified a significant organic component in primary and secondary aerosols. Comparison of SOAP aerosol number and size distributions reveals an underprediction in GLOMAP (GLObal Model of Aerosol Processes)-mode aerosol number in clean marine air masses, suggesting a missing marine aerosol source in the model. The SOAP data will be further examined for evidence of nucleation events and also to identify relationships between MBL composition and surface ocean biogeochemistry that may provide potential proxies for aerosol precursors and production.