Passive groundwater sampling is defined as the collection of a water sample from a well without the use of purging by a pump or retrieval by a bailer (Interstate Technology and Regulatory Council [ITRC], 2006; American Society for Testing and Materials [ASTM], 2014). No purging means that advection of water is not involved in collecting the water sample from the well. Passive samplers rely on diffusion as the primary process that drives their collection of chemical constituents. Diffusion is the transport of chemicals caused by the presence of a chemical gradient. Chemicals tend to move or diffuse from areas of higher concentration to areas of lower concentration to reach an average or equilibrium concentration. Passive sampling of groundwater relies on the ambient exchange of groundwater in the formation with water in the screened or open interval of a well. In this report, the term formation is used to describe all saturated hydrogeologic units that yield water to a well. If the well opening is unclogged and free of a film of deposits from physical turbidity or chemical precipitation, then the exchange of groundwater is likely adequate, and the water in the open interval will be representative of water in the formation. In some cases, the passive sample from the well opening can be more representative of groundwater from the formation than a sample collected by pumping if pumping induces mixing of water in the open interval with stagnant casing water that has undergone chemical alteration (Harte and others, 2018). In most cases, passive sampling will better represent the ambient groundwater chemistry flowing through the open interval of a well because pumping may capture water of different chemistry from downgradient or lateral areas that would not normally pass through the well. Three basic types of passive samplers are discussed in this report. The first type of passive sampler is the equilibrium-membrane type, which includes a semi-permeable membrane through which chemicals diffuse or permeate. Permeation is simply the process of water or chemicals moving through openings in the membrane. The authors contend that permeation is dominated by diffusion for many of the passive samplers discussed in this report. Some passive equilibrium-membrane-type samplers allow most types of chemical constituents through, whereas others allow the diffusion of only selected groups of chemicals. Once the chemical constituents are inside the membrane, they are retained by the equilibration of concentrations inside the sampler with those outside the sampler. The second type of passive sampler is an equilibrium-thief type, which has no semi-permeable membrane. Chemical constituents simply move through the openings in the body of the sampler either initially through advection and dispersion or over time primarily by diffusion. Chemical constituents reach equilibrium between the water in the sampler and the water in the well and are captured in the sampler when the sampler is closed. The third type of passive sampler is an accumulation-type sampler that contains sorptive media. Selected chemical constituents are sorbed onto the media that the sampler contains for later extraction and analysis. Although passive samplers have been available for more than 15 years (from present [2020]), their use by U.S. Geological Survey (USGS) hydrologists and hydrologic technicians to monitor groundwater quality largely has been limited to selected research studies. The authors believe that this may be the result of (1) a lack of exposure of most USGS personnel to passive samplers and the uses of these samplers and (2) the lack of a USGS-approved protocol for the proper use of these samplers by USGS personnel. This report is an effort to fill those two needs. The focus of this report is on hydraulic, hydrologic, and chemical considerations in the application of passive samplers and interpretation of groundwater chemistry results obtained using passive samplers in wells. This report describes the differences between purging and passive sampling methods in groundwater and explains how and why passive samplers work. The report points out the advantages and limitations of passive samplers in general and for each particular type of passive sampler. Important considerations to be taken into account prior to the use of passive samplers are discussed, such as defining the data-quality objectives, the water-quality constituents to be sampled, sample volumes required for analysis, well construction of the sampling network, and the geologic formations that will be sampled. Potential applications of passive samplers also are discussed, such as chemical-vertical profiling of wells. A general field protocol for the deployment, recovery, and sample collection using these devices is described, and some overall guidance for the practitioner with application examples is given. Comparison methods used to evaluate results from passive sampling versus purge sampling also are discussed.