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There are two types of puzzles for babies and toddlers - large, foam mats that function as a soft floor surface, and large-piece cardboard or wood puzzles. The former can easily be replaced with an area rug if desired. For the latter - puzzles intended to promote development through gross and fine motor skill - there are a wide array of options and things to consider.
Foam puzzles are typically made of EVA - ethylene vinyl acetate - which in itself is fairly benign, though petroleum-based. However, some tests have found that some EVA foam releases formamide, a carcinogen. Puzzles made of wood may contain formaldehyde in the adhesives.
As always with babies and young children, make sure pieces are large and in good condition so that they are not choking hazards - because babies will put anything they can pick up or reach into their mouths. Puzzles should be kept clean, as household dust can contain a host of hazards.
Solid wood puzzles with non-toxic paints and finishes are best for babies. If you choose a puzzle made with plywood, laminate, or MDF, ask about VOCs and formaldehyde - and seek those that are certified to CARB (California Air Resources Board) Phase 2 limits. Shopping on a tight budget? Look for used puzzles made after 2008. Formaldehyde levels drop after six to ten months.