Ingestion of food contaminated by bacteria, viruses, parasites or chemical substances is responsible for the illness or death of about one in ten people worldwide every year. This characterizes significant public health risks, in addition to raising annual public health costs. Metals and metalloids are noteworthy among chemical environmental contaminants, due to their environmental persistence, bioaccumulation and, in some cases, biomagnification capacity, as well as high toxicity risks. Several elements have been detected in high concentrations in the environment due to anthropogenic activities, leading to trophic chain incorporation and aquatic organism bioaccumulation, such as fish and mussels. These organisms, in turn, play extremely important ecological roles in aquatic trophic webs as energy carriers to higher trophic levels, becoming important links between the environment, contaminants and human populations through their consumption. In Brazil, several protected area categories have been established, including Extractive Reserves (RESEX). These are used by traditional populations whose survival is based on the extraction of natural resources and on subsistence and small animal agricultural activities. One of these RESEX, located in the Região dos Lagos area, in the state of Rio de Janeiro, comprises the Arraial do Cabo Marine Extractive Reserve, the first Marine Extractive Reserve in Brazil, created in 1997. Unfortunately, however, aquatic organisms in this RESEX have been shown to be contaminated by high metal and metalloid concentrations, mainly arsenic (As), often exceeding limits established by Brazilian and international legislations. This may make one of the main local economic activities, artisanal fishing, unfeasible, leading to socio-economic and environmental concerns, as this activity is an important food and economic source, representing over 50 % of the national fishery production, reaching 70 % in certain regions. In addition, ecosystem degradation heavily impacts poor populations, such as fishers, who are very vulnerable to ecosystem changes, including the degradation of fishing resources, leading to decreased protein intake by vulnerable populations and the consumption of food items containing high contaminant levels. In this context, this chapter will discuss aquatic organism contamination by As, focusing on the Arraial do Cabo RESEX, an important Brazilian conservation area, including chemical (i.e. As speciation into organic and inorganic forms) and geochemical As aspects, food chain accumulation capacity, potential effects on biota and humans and possible local traditional fishing community outcomes, categorized as extremely vulnerable by Brazilian legislation.