In the environment, simultaneous presence of arsenic (As) of different oxidation states is common, which hampers our understanding of As behavior. In the current study, the pH dependency of arsenite (As(III)) and arsenate (As(V)) adsorption to goethite under the influence of calcium (Ca2+) (as a major cation) and phosphate (PO43-) (as a major anion) was studied, and the reliability of the CD-MUSIC model prediction was tested. The results show that the presence of the major ions led in general to a weaker and more complicated pH dependency of As adsorption. Calcium promoted As(V) adsorption especially at high pH, which can reverse the direction of the pH dependency. The presence of Ca2+ can even decrease As(III) adsorption when As(V) and/or PO43- are present. Phosphate competed strongly with both As(III) and As(V) in their adsorption, especially at intermediate and low pH. In the multi-component system, As(III) adsorbs weaker than As(V) over the environmental relevant pH range, therefore it is often the dominant As species in solution and soluble As(III) concentration generally decreases with increasing pH. In the same pH range, As(V) adsorption shows a complicated pH dependency. Soluble As(V) reaches a minimum around pH 6 at high concentration of major bivalent cations (e.g. Ca2+), whereas soluble As(V) will decrease with pH at low bivalent cation concentrations. The experimental results can be reliably predicted and explained with the CD-MUSIC model. The outcome of this study can provide understanding needed in the risk assessment and remediation of As contaminated soils and water.