Whether correcting deficiencies with whole foods alone is possible depends on many factors: how bad the deficiencies are, which minerals are deficient, your health status, environmental conditions, etc. For example, if you live in an area with selenium-poor soils, and that's your only deficiency, then eating whole foods that contain selenium should be enough. But if you're unhealthy and have a number of deficiencies that have advanced to the point where your ability to absorb nutrients from your food is impaired, then food alone may not be enough.
There are things you can do to improve how well nutrients are absorbed from your food. As I've mentioned before, chewing really well is an important one. Eating a good variety of food is another (avoid a mono-diet). Juicing (veggie juices) can also help.
I tried a whole food approach for quite a while, without supplementation, and it wasn't enough for me--but I was very unwell at the time. I had to add supplements before I started to make any progress. In fact, after everything corrected, I stopped taking supplements and went back to whole foods only, and found that several minerals in my blood dropped back down well below normal. So for me, I need to continue certain supplements even today.
One issue with using whole foods alone is that there can be considerable
variation in the mineral content of your food. Also, certain types of food are good sources for certain minerals; if you eliminate those foods from your diet, it can be a challenge to get enough of the associated minerals. For example, molybdenum is present in beans; if you don't eat beans, it can be difficult to get enough.
Of course, if you're healthy and live in good environment, I don't think
this is an issue. Paleo people certainly didn't need supplements to survive and thrive.
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