Ling Jin

Pharmaceuticals in Tap Water: Human Health Risk Assessment and Proposed Monitoring Framework in China

Background: Pharmaceuticals are known to contaminate tap water worldwide, but the relevant human health risks have not been assessed in China. Objectives: We monitored 32 pharmaceuticals in Chinese tap water and evaluated the life-long human health risks of exposure in order to provide information for future prioritization and risk management. Methods: We analyzed samples (n = 113) from 13 cities and compared detected concentrations with existing or newly-derived safety levels for assessing risk quotients (RQs) at different life stages, excluding the prenatal stage. Results: We detected 17 pharmaceuticals in 89% of samples, with most detectable concentrations (92%) at < 50 ng/L. Caffeine (median–maximum, nanograms per liter: 24.4–564), metronidazole (1.8–19.3), salicylic acid (16.6–41.2), clofibric acid (1.2–3.3), carbamazepine (1.3–6.7), and dimetridazole (6.9–14.7) were found in ≥ 20% of samples. Cities within the Yangtze River region and Guangzhou were regarded as contamination hot spots because of elevated levels and frequent positive detections. Of the 17 pharmaceuticals detected, 13 showed very low risk levels, but 4 (i.e., dimetridazole, thiamphenicol, sulfamethazine, and clarithromycin) were found to have at least one life-stage RQ ≥ 0.01, especially for the infant and child life stages, and should be considered of high priority for management. We propose an indicator-based monitoring framework for providing information for source identification, water treatment effectiveness, and water safety management in China. Conclusion: Chinese tap water is an additional route of human exposure to pharmaceuticals, particularly for dimetridazole, although the risk to human health is low based on current toxicity data. Pharmaceutical detection and application of the proposed monitoring framework can be used for water source protection and risk management in China and elsewhere.

Applicability of passive sampling to bioanalytical screening of bioaccumulative chemicals in marine wildlife.

Quantification of bioaccumulative contaminants in biota is time and cost-intensive and the required extensive cleanup steps make it selective toward targeted chemical groups. Therefore tissue extracts prepared for chemical analysis are not amenable to assess the combined effects of unresolved complex mixtures. Passive equilibrium sampling with polydimethylsiloxane (PDMS) has the potential for unbiased sampling of mixtures, and the PDMS extracts can be directly dosed into cell-based bioassays. The passive sampling approach was tested by exposing PDMS to lipid-rich tissue (dugong blubber; 85% lipid) spiked with a known mixture of hydrophobic contaminants (five congeners of tetra- to octachloro-dibenzo-p-dioxins). The equilibrium was attained within 24 h. Lipid-PDMS partition coefficients (Klip-PDMS) ranged from 20 to 38, were independent of hydrophobicity, and within the range of those previously measured for organochlorine compounds. To test if passive sampling can be combined with bioanalysis without the need for chemical cleanup, spiked blubber-PDMS extracts were dosed into the CAFLUX bioassay, which specifically targets dioxin-like chemicals. Small quantities of lipids coextracted by the PDMS were found to affect the kinetics in the regularly applied 24-h bioassay; however, this effect was eliminated by a longer exposure period (72 h). The validated method was applied to 11 unspiked dugong blubber samples with known (native) dioxin concentrations. These results provide the first proof of concept for linking passive sampling of lipid-rich tissue with cell-based bioassays, and could be further extended to other lipid rich species and a wider range of bioanalytical end points.

Understanding bioavailability and toxicity of sediment‐associated contaminants by combining passive sampling with in vitro bioassays in an urban river catchment

Bioavailable and bioaccessible fractions of sediment-associated contaminants are considered as better dose metrics for sediment-quality assessment than total concentrations. The authors applied exhaustive solvent extraction and nondepletive equilibrium sampling techniques to sediment samples collected along the Brisbane River in South East Queensland, Australia, which range from pristine environments to urban and industry-impacted areas. The wide range of chemicals expected prevents comprehensive chemical analysis, but a battery of cell-based bioassays sheds light on mixture effects of chemicals in relation to various modes of toxic action. Toxic effects were expressed as bioanalytical equivalent concentrations (BEQs) normalized to the organic carbon content of each sediment sample. Bioanalytical equivalent concentrations from exhaustive extraction agreed fairly well with values estimated from polydimethylsiloxane passive sampling extracts via the constant organic carbon to polydimethylsiloxane partition coefficient. Agreement was best for bioassays indicative of photosynthesis inhibition and oxidative stress response and discrepancy within a factor of 3 for the induction of the aryl hydrocarbon receptor. For nonspecific cytotoxicity, BEQ from exhaustive extraction were 1 order of magnitude higher than values from equilibrium sampling, possibly because of coextraction of bioactive natural organic matter that led to an overestimation of toxicity in the exhaustive extracts, which suggests that passive sampling is better suited in combination with bioanalytical assessment than exhaustive extraction.

Coupling passive sampling with in vitro bioassays and chemical analysis to understand combined effects of bioaccumulative chemicals in blood of marine turtles

Conventional target analysis of biological samples such as blood limits our ability to understand mixture effects of chemicals. This study aimed to establish a rapid passive sampling technique using the polymer polydimethylsiloxane (PDMS) for exhaustive extraction of mixtures of neutral organic chemicals accumulated in blood of green turtles, in preparation for screening in in vitro bioassays. We designed a PDMS-blood partitioning system based on the partition coefficients of chemicals between PDMS and major blood components. The sampling kinetics of hydrophobic test chemicals (polychlorinated dibenzo-p-dioxins; PCDDs) from blood into PDMS were reasonably fast reaching steady state in <96 h. The geometric mean of the measured PDMS-blood partition coefficients for PCDDs, polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) was 14 L blood kg PDMS(-1) and showed little variability (95% confidence interval from 8.4 to 29) across a wide range of hydrophobicity (logKow 5.7-8.3). The mass transfer of these chemicals from 5 mL blood into 0.94 g PDMS was 62-84%, which is similar to analytical recoveries in conventional solvent extraction methods. The validated method was applied to 15 blood samples from green turtles with known concentrations of PCDD/Fs, dioxin-like PCBs, PBDEs and organochlorine pesticides. The quantified chemicals explained most of the dioxin-like activity (69-98%), but less than 0.4% of the oxidative stress response. The results demonstrate the applicability of PDMS-based passive sampling to extract bioaccumulative chemicals from blood as well as the value of in vitro bioassays for capturing the combined effects of unknown and known chemicals.

Bioanalytical Approaches to Understanding Toxicological Implications of Mixtures of Persistent Organic Pollutants in Marine Wildlife

Compelling evidence documents that chemical pollution, including exposure to persistent organic pollutants (POPs), plays an important role in marine wildlife health. The link between the burden of disease and the burden of POPs in marine wildlife species is not well established. To address this challenge, tools are needed for the mechanistic and quantitative understanding of chemical exposure and its toxicological implications. This chapter reviews the current approaches and points out the need for a more integrated methodological framework for linking chemical exposure and mixture effects. The existing extraction methods and targeted nature of chemical analysis have limited our capability of assessing the entire mixture of POPs as an entity, thus warranting continuous development of quantitative, unbiased sampling techniques. On the other hand, we need further mechanistic, quantitative understanding of biological pathways linking chemical exposure to adverse health outcomes to design a focused, meaningful test battery of bioassays for the comprehensive toxicological profiling of POP mixtures. These advances will be an important step toward understanding the contribution of POPs to the overall impact of environmental threats on marine wildlife population health, which will in turn inform management options for wildlife conservation.