Pharmaceuticals and personal care products in biosolids/sewage sludge: the interface between analytical chemistry and regulation.

Modern sanitary practices result in large volumes of human waste, as well as domestic and industrial sewage, being collected and treated at common collection points, wastewater treatment plants (WWTPs). In recognition of the growing use of sewage sludge as fertilizers and soil amendments, and the scarcity of current data regarding the chemical constituents in sewage sludge, the US National Research Council (NRC) in 2002 produced a report on sewage sludge. Among the NRC's recommendations was the need for investigating the occurrence of pharmaceuticals and personal care products (PPCPs) in sewage sludge. PPCPs are a diverse array of non-regulated contaminants that had not been studied in previous sewage sludge surveys but which are likely to be present. The focus of this paper will be to review the current analytical methodologies available for investigating whether pharmaceuticals are present in WWTP-produced sewage sludge, to summarize current regulatory practices regarding sewage sludge, and to report on the presence of pharmaceuticals in sewage sludge.

Chemical markers of human waste contamination: analysis of urobilin and pharmaceuticals in source waters.

Giving public water authorities another tool to monitor and measure levels of human waste contamination of waters simply and rapidly would enhance public protection. Most of the methods used today detect such contamination by quantifying microbes occurring in feces in high enough densities that they can be measured easily. However, most of these microbes, for example E. coli, do not serve as specific markers for any one host species and many can have origins other than feces. As an alternative, chemicals shed in feces and urine might be used to detect human waste contamination of environmental waters. One potential chemical marker of human waste is the compound urobilin. Urobilin is one of the final by-products of hemoglobin breakdown. Urobilin is excreted in both the urine and feces from many mammals, particularly humans. Source waters from 21 sites in New England, Nevada, and Michigan were extracted using hydrophilic-lipophilic balance (HLB) cartridges and then analyzed by high performance liquid chromatography-electrospray mass spectrometry (HPLC-ES-MS). As a marker of human waste, urobilin was detected in many of the source waters at concentrations ranging from not detectable to 300 ng L(-1). Besides urobilin, azithromycin, an antibiotic widely prescribed for human use only in the US, was also detected in many of these waters, with concentrations ranging from not detectable to 77 ng L(-1). This methodology, using both urobilin and azithromycin (or any other human-use pharmaceutical) could be used to give public water authorities a definitive method for tracing the sources of human waste contamination. The analysis and detection of urobilin in surface waters by HPLC-ES-MS has not been previously reported in the peer-reviewed literature.

Polar organic chemical integrative sampling and liquid chromatography-electrospray/ion-trap mass spectrometry for assessing selected prescription and illicit drugs in treated sewage effluents.

The purpose of the research presented in this paper was twofold: (1) to demonstrate the coupling of two state-of-the-art techniques: a time-weighted polar organic chemical integrative sampler (POCIS) and microliquid chromatography-electrospray/ion-trap mass spectrometry and (2) to assess the ability of these methodologies to detect six drugs (azithromycin, fluoxetine, omeprazole, levothyroxine, methamphetamine, methylenedioxymethamphetamine [MDMA]) in a real-world environment, e.g., waste water effluent. In the effluent from three wastewater treatment plants (WWTPs), azithromycin was detected at concentrations ranging from 15 to 66 ng/L, which is equivalent to a total annual release of 1 to 4 kg into receiving waters. Detected and confirmed in the effluent from two WWTPs were two illicit drugs, methamphetamine and MDMA, at 2 and 0.5 ng/L, respectively. Although the ecotoxicologic significance of drugs in environmental matrices, particularly water, has not been closely examined, it can only be surmised that these substances have the potential to adversely affect biota that are continuously exposed to them even at very low levels. The potential for chronic effects on human health is also unknown but of increasing concern because of the multiuse character of water, particularly in densely populated, arid areas.

Monitoring dibutyltin and triphenyltin in fresh waters and fish in the United States using micro-liquid chromatography-electrospray/ion trap mass spectrometry.

There is a growing body of evidence that toxic organotins are making their way into terrestrial and aquatic mammals including humans. In the United States, one possible route of environmental exposure to organotins (specifically dibutyltin and triphenyltin) is via fresh surface waters and fish taken from those waters. A unique methodology was used for quantitative and speciation of the organotins. This green-chemistry method combines two extraction techniques (solid-phase extraction for waters; hexane/tropolone extraction for fish) with micro-liquid chromatography-electrospray/ion trap mass spectrometry (micro-LC-ES/ITMS) as the detection method. A small survey looking for organotins in fresh surface waters across the United States, and fish from those waters, was conducted. Various concentrations of dibutyltin and triphenyltin were detected in fresh water, ranging from nondetect to 2 ppb, and nondetect to 6 ppb, respectively. In fish dibutyltin and triphenyltin were detected from nondetect to 200 ppb, and nondetect to 400 ppb, respectively.

A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants.

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.