Distribution and Speciation of Arsenic in Temperate Marine Saltmarsh Ecosystems

Environmental Context. The pathways by which arsenic is accumulated and transferred in aquatic ecosystems are relatively unknown. Examination of whole marine ecosystems rather than individual organisms provides greater insights into the biogeochemical cycling of arsenic. Saltmarshes with low ecological diversity are an important terrestrial–marine interface about which little is known regarding arsenic concentrations and species distribution. This study examines the cycling of arsenic within Australian saltmarsh ecosystems to further understand its distribution and trophic transfer. Abstract. This paper reports the distribution of total arsenic and arsenic species in saltmarsh ecosystems located in south-east Australia. We also investigated the relationship between arsenic, iron, and phosphorus concentrations in saltmarsh halophytes and associated sediment. Total mean arsenic concentrations in saltmarsh plants, S. quinqueflora and S. australis, for leaves ranged from 0.03 ± 0.05 to 0.67 ± 0.48 μg g−1 and 0.03 ± 0.02 to 0.08 ± 0.06 μg g−1, respectively, and for roots ranged from 2 ± 2 to 6 ± 12 μg g−1 and 0.39 ± 0.20 to 0.57 ± 1.06 μg g−1 respectively. Removal of iron plaque from the roots reduced the arsenic concentration variability to 0.40–0.79 µg g−1 and 0.95–1.05 µg g−1 for S. quinqueflora and S. australis roots respectively. Significant differences were found between locations for total arsenic concentrations in plant tissues and these differences could be partially attributed to differences in sediment arsenic concentrations between locations. For S. quinqueflora but not S. australis there was a strong correlation between arsenic and iron concentrations in the leaf and root tissues. A significant negative relationship between arsenic and phosphorus concentrations was found for S. quinqueflora leaves but not roots. Total mean arsenic concentrations in salt marsh animal tissues (7 ± 2–21 ± 13 µg g−1) were consistent with those found for other marine animals. The concentration of total arsenic in gastropods and amphipods could be partially explained by the concentration of total arsenic in the dominant saltmarsh plant S. quinqueflora. Of the extractable arsenic, saltmarsh plants were dominated by arsenic(iii), arsenic(v) (66–99%), and glycerol arsenoribose (17–35%). Arsenobetaine was the dominant extractable arsenic species in the gastropods Salinator soilda (84%) and Ophicardelus ornatus (89%) and the crab Neosarmatium meinerti (89%). Amphipods contained mainly arsenobetaine (44%) with some phosphate arsenoribose (23%). Glycerol trimethyl arsonioribose was found in both gastropods (0.7–0.8%) and the visceral mass of N. meinerti (0.1%). These results show that arsenic uptake into plants from uncontaminated saltmarsh environments maybe dependent on plant iron uptake and inhibited by high phosphorus concentrations. Arsenic in saltmarsh plants is mainly present as inorganic arsenic, but arsenic in animals that eat plant detritus is present as organo arsenic species, primarily arsenobetaine and arsenosugars. The presence of glycerol trimethyl arsonioribose poses the question of whether trimethylated arsonioriboses are transitory intermediates in the formation of arsenobetaine.