The emergence of stable isotopes in environmental and forensic geochemistry studies: a review

In the past decade, environmental forensics has emerged as a discipline directed toward determining parties liable for causing spills of contaminants into the environment. Such investigations, while geared toward determining the guilty parties in order to recover costs of the cleanup and remediation, require various questions to be addressed. These include determination of the nature of the product; Where did it come from?; Extent of weathering, if any; How long has it been there?; and Is it degrading naturally? Traditionally, these studies have been addressed through utilization of techniques such as gas chromatography (GC) and gas chromatography–mass spectrometry (GCMS). However, in recent years, stable isotopes, primarily determined through the use of combined gas chromatography–isotope ratio mass spectrometry (GCIRMS), have emerged as an equally important tool in environmental forensics. For relatively low molecular, volatile compounds such as MTBE, BTEX, or chlorinated solvents, the isotopes, primarily carbon and hydrogen, have been used extensively for evaluating the onset of natural attenuation. For larger molecules such as PCBs or PAHs, in which the effects of biodegradation on the isotope composition of these molecules is minimal, the isotopic fingerprints of the individual compounds can be used for correlation purposes. In this paper, a brief introduction to isotope geochemistry will be given, followed by a review of applications of stable isotopes to a variety of environmental problems. While the review may not necessarily be exhaustive, it will provide a comprehensive overview of areas where isotopes have been used and potential applications for the future. Most of the review is concerned with carbon and hydrogen isotopes, although a brief overview of the emerging area of chlorine isotopes will also be discussed.     

Are dispersion models suitable for simulating small gaseous chlorine releases?

Dispersion models are mostly validated on the basis of historical dispersion experiments. The latter imply large quantities of hazardous products (flammable or toxic gases), and are dedicated to study the dispersion of the resulting clouds on great distances from the source to reach a better knowledge of the different phases of gas dispersion (slumping, creeping, passive dispersion…).However, dispersion models have hardly been validated on small releases and therefore require more validation on small plumes of dangerous gases. Indeed, what is their reliability in case of accidents involving small amounts (e.g., chlorine leakages at swimming pools’ installations), and for small distances downwind the gas source? This information is of prime interest in so far as small releases are more likely to occur than larger ones.This paper reports on chlorine small-scale dispersion experiments and deals with the comparison between experimental data of ground level concentrations in the plume and predicted concentrations obtained from several dispersion models.     

Improved quartz furnace method for chlorine and sulfur determination in municipal solid waste

 A method of determining the chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) was studied. The quartz furnace method was improved in two ways: recovery from ash by hot extraction with dilute nitric acid, and avoidance of the volatilization of alkali (earth) metal chlorides by setting the sample combustion temperature at 600°C. In a comparison with the bomb method, using nine sets of kitchen garbage and waste plastics, the bomb method yielded a 15%–25% lower value than the improved quartz furnace method. Combustion in the bomb was frequently incomplete, resulting in recovery losses of Cl and S. The average kitchen garbage involved 5.2 mg Cl/g, of which at least 24.1% would be converted to HCl. Plastics contained 23 mg Cl/g generating 88.1% HCl on average. In the same way, kitchen garbage contained 3.0 mg S/g, generating 52.3% SO _x , whereas plastics contained 1.1 mg S/g with 55.1% SO _x formation. Received: March 20, 2002 / Accepted: October 13, 2002     

Drawing the Battle Lines: Tracing the “Science War” in the Construction of the Chloroform and Human Health Risks Debate

The United States Environmental Protection Agency (US EPA) and the Chlorine Chemistry Council, the Chemical Manufacturers Association, and others have been embroiled in a legal challenge concerning the US EPA's “reversal” regarding the scientific assessment of chloroform's carcinogenicity. This issue arose during the US EPA's November 1998 promulgation of a Maximum Contaminant Level Goal for chloroform in the Stage 1 Final Rules for Disinfectants and Disinfection Byproducts in drinking water. In this paper we adopt a claimsmaking approach: to trace the development and outcome of the chloroform court challenge in the USA, to examine the construction of scientific knowledge claims concerning chloroform risk assessments, and to investigate how different interpretations of scientific uncertainties regarding the evidence are contested when such uncertainties are brought into a regulatory and judicial arena. This “science war” (Chlorine Chemistry Council and others v. US EPA and others) took place in the US Court of Appeals for the District of Columbia Circuit. The scientific “authority” in the construction of scientific claims in this dispute is based on the International Life Sciences Institute expert panel report on chloroform. Examining these science wars is important because they signal critical shifts in science policy agendas. The regulatory outcome of the chloroform science war in the United States can have profound implications for the construction and acceptance of scientific claims regarding drinking water in other jurisdictions (e.g., Canada). In this challenge, we argue that the actors involved in the dispute constructed “boundaries” around accepted and credible scientific claims.     

Controlling substance flows: The case of chlorine

The contribution of chlorinated hydrocarbons (CHCs) to environmental problems in the Netherlands is discussed in an economic context. The economic interactions within the chlorine market, including the link to caustic soda production, are described, and PVC is taken as a case study. Key policy options are evaluated in terms of their potential for environmental improvement. It appears that 95% of CHC emissions causing environmental problems are due to dissipative applications. With respect to the specific problems of ozone depletion and global warming, only a small group of compounds is responsible for most of the impact. Moreover, economic interactions within the group of CHCs can strongly influence the net effect of environmental policy measures. Policies aimed at a reducing volume output of certain specific groups of CHCs will inevitably lead to trade-offs between environmental problems. The environmental impact of a hypothetical ban on CHCs is discussed in relation to the use of PVC as a sink for chlorine. Both these options appear to have drawbacks. Moreover, no absolute conclusion can be drawn until the environmental impact of CHC substitutes is known.     

自来水厂液氯贮罐氯气泄漏事故风险评价初探

针对自来水厂液氯贮罐发生泄露的事故风险,应用烟团模式进行了液氯泄露后污染物浓度预测,并根据预测浓度从环境标准和化学物质危险度两方面进行了事故风险评价探讨,得出致死风险.     

氯对医疗废物处置厂废水处理的影响

分析了医疗废物处置厂废水处理中如何消减氯对后续活性污泥处理工艺负面影响的问题。结合山西省某医疗废物高温蒸汽灭菌厂的废水处理实例,提出了一种利用生活污水中的氨氮来消减余氯对后续活性污泥处理影响的有效方法。     

Chlorine promotes antimony volatilization in municipal waste incineration

Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb₄O₆) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb₄O₆ occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl₂, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999     

Assessment of water pollution in different bleaching based paper manufacturing and textile dyeing industries in India

Paper industries using different raw materials such as hard wood, bamboo, baggase, rice-straw and waste papers and bleaching chemicals like chlorine, hypochlorite, chlorine dioxide, hydrogen peroxide, sulphite and oxygen were studied to estimate organic pollution load and Adsorbable Organic Halides (AOX) per ton of production. The hard wood based paper industries generate higher Chemical Oxygen Demand (COD) loads (105–182 kg t⁻¹) and Biochemical Oxygen Demand (BOD) loads (32.0–72 kg t⁻¹) compared to the agro and waste paper based industrial effluents. The bleaching sequences such as C–EP–H–H, C–E–H–H, C–E–Do–D1 and O–Do–EOP–D1 are adopted in the paper industries and the molecular elemental chlorine free bleaching sequence discharges low AOX in the effluent. The range of AOX concentration in the final effluent from the paper industries was 0.08–0.99 kg t⁻¹ of production. Water consumption was in the range of 100–130 m³ t⁻¹ of paper production for wood based industries and 30–50 m³ for the waste paper based industries. Paper machine effluents are partially recycled after treatment and pulp mill black liquor are subject to chemical recovery after evaporation to reduce the water consumption and the total pollution loads. Hypochlorite bleaching units of textile bleaching processes generate more AOX (17.2–18.3 mg l⁻¹) and are consuming more water (45–80 l kg⁻¹) whereas alkali peroxide bleaching hardly generates the AOX in the effluents and water consumption was also comparatively less (40 l kg⁻¹ of yarn/cloth).     

Chlorine emission during the chlorination of water – case study

This paper deals with the incident of the excessive use of chlorine and leakage of unused chlorine from an industrial chlorination cistern and the lesson learned.