Indicators for Chemicals: Sources,impacts and policy performance (5 pp)

Background Different types of indicators have been developed to describe the impact of chemicals on society and environment. Due to the high number of substances and their different types of use, most of these indicators are directed to specific areas of interest – regarding workplace safety, environmental health or consumer health. They address a specific subset of chemicals and can be used for monitoring enterprise-specific, national or international management measures. Main Features A survey of existing indicators for chemicals has shown that indicators already exist for a remarkable number of problem fields. As soon as the release and the environmental fate of chemicals are taken into account, the complexity of the approaches increases considerably. The distinction between indicators for drivers, pressures, state, impacts and responses, as proposed by the European Environmental Agency, supports the identification of proper indicators for a specific type of problem. Discussion and Conclusions. No single indicator exists which is able to cover the whole range of chemicals and their applications. Several indicator approaches cover at least a subset of the most relevant substances. If they are intended to be used for European monitoring, robust data must be provided by EU Member States. Chemicals in enterprises (ancillary inputs as well as process chemicals) are an important element of in-plant material flow management – in terms of occupational safety and health as well as environmental protection. Existing indicators for hazardous chemicals can be a valuable tool for process and product refinement regarding hazardous chemicals, especially for enterprises. Outlook Indicators for production and impact of chemicals, as well as policy performance indicators, are essential elements in order to monitor the management of chemicals. They have to be established for the national and for the EU level.     

Non-regulated water contaminants: emerging research

Those chemical pollutants that are regulated under various international, federal, and state programs represent but a small fraction of the universe of chemicals that occur in the environment as a result of both natural processes and human influence. Although the number of these targeted chemicals might be minuscule compared with the universe of both known and yet-to-be identified chemicals, an implicit assumption is that these selective lists of chemicals are responsible for the most significant share of risk with respect to environmental or economic impairment or to human health. This paper examines some of the less-discussed aspects of the background and assumptions that underlie society's relationship with chemical pollutants in water, particularly with respect to the need for a more holistic understanding of exposure and risk.     

Green chemistry

A grand challenge facing government, industry, and academia in the relationship of our technological society to the environment is reinventing the use of materials. To address this challenge, collaboration from an interdisciplinary group of stakeholders will be necessary. Traditionally, the approach to risk management of materials and chemicals has been through inerventions intended to reduce exposure to materials that are hazardous to health and the environment. In 1990, the Pollution Prevention Act encouraged a new tact-elimination of hazards at the source. An emerging approach to this grand challenge seeks to embed the diverse set of environmental perspectives and interests in the everyday practice of the people most responsible for using and creating new materials—chemists. The approach, which has come to be known as Green Chemistry, intends to eliminate intrinsic hazard itself, rather than focusing on reducing risk by minimizing exposure. This chapter addresses the representation of downstream environmental stakeholder interests in the upstream everyday practice that is reinventing chemistry and its material inputs, products, and waste as described in the “12 Principles of Green Chemistry”.     

祁连山东端地表及地下水水化学时空变化特征

于2016~2017年5~9月采集祁连山东端（乌鞘岭、古浪、天祝）的地表水和地下水样品进行水化学分析,综合运用统计分析、Piper三线图、Gibbs图以及离子比值等方法探究了祁连山东端地表水和地下水主要离子组成特征、来源以及时空变化.结果表明,祁连山东端地表水和地下水化学组成中优势阳离子为Ca²⁺和Na⁺,Ca²⁺的平均浓度为76.897mg/L,占比73.89%;Na⁺的浓度为16.592mg/L,占比15.94%.优势阴离子为HCO₃^-和SO₄^2-,HCO₃^-浓度190.117mg/L,占比68.71%;其次是SO₄^2-,平均值为67.565mg/L,占比为24.42%.乌鞘岭河水、地下水,天祝河水、地下水的水化学类型为HCO₃^--Ca²⁺型,古浪河水、地下水水化学类型为HCO₃^--Ca²⁺-Mg²⁺型,处于水化学易变区.不同水体离子来源于岩石风化,主要受碳酸盐与硅酸盐风化溶解共同作用控制,人类活动在一定程度上贡献了水体的离子来源.不同水体主要离子浓度的时间变化特征各不相同,整体上大部分水体的离子浓度随时间变化不明显,总体趋势较平缓.     

Spatial Convergence in Major Dissolved Ion Concentrations and Implications of Headwater Mining for Downstream Water Quality

Spatial patterns in major dissolved solute concentrations were examined to better understand impact of surface coal mining in headwaters on downstream water chemistry. Sixty sites were sampled seasonally from 2012 to 2014 in an eastern Kentucky watershed. Watershed areas (WA) ranged from 1.6 to 400.5 km² and were mostly forested (58%–95%), but some drained as much as 31% surface mining. Measures of total dissolved solutes and most component ions were positively correlated with mining. Analytes showed strong convergent spatial patterns with high variability in headwaters (<15 km² WA) that stabilized downstream (WA > 75 km²), indicating hydrologic mixing primarily controls downstream values. Mean headwater solute concentrations were a good predictor of downstream values, with % differences ranging from 0.55% (Na⁺) to 28.78% (Mg²⁺). In a mined scenario where all headwaters had impacts, downstream solute concentrations roughly doubled. Alternatively, if mining impacts to headwaters were minimized, downstream solute concentrations better approximated the 300 μS/cm conductivity criterion deemed protective of aquatic life. Temporal variability also had convergent spatial patterns and mined streams were less variable due to unnaturally stable hydrology. The highly conserved nature of dissolved solutes from mining activities and lack of viable treatment options suggest forested, unmined watersheds would provide dilution that would be protective of downstream aquatic life.     

Toward Explaining Nitrogen and Phosphorus Trends in Chesapeake Bay Tributaries, 1992–2012

Understanding trends in stream chemistry is critical to watershed management, and often complicated by multiple contaminant sources and landscape conditions changing over varying time scales. We adapted spatially referenced regression (SPARROW) to infer causes of recent nutrient trends in Chesapeake Bay tributaries by relating observed fluxes during 1992, 2002, and 2012 to contemporary inputs and watershed conditions. The annual flow‐normalized nitrogen flux to the bay from its watershed declined by 14% to 127,000 Mg (metric tons) between 1992 and 2012, due primarily (more than 80% of the decline) to reduced point sources. The remainder of the decline was due to reduced atmospheric deposition (13%) and urban nonpoint sources. Agricultural inputs, which contribute most nitrogen to the bay, changed little, although trends in the average nitrogen yield (flux per unit area) from cropland and pasture to streams in some settings suggest possible effects of evolving nutrient applications or other land management practices. Point sources of phosphorus to local streams declined by half between 1992 and 2012, while nonpoint inputs were relatively unchanged. Annual phosphorus delivery to the bay increased by 9% to 9,570 Mg between 1992 and 2012, however, due mainly to reduced retention in the Susquehanna River at Conowingo Reservoir.     

Methylated and thiolated arsenic species for environmental and health research——A review on synthesis and characterization

Hundreds of millions of people around the world are exposed to elevated concentrations of inorganic and organic arsenic compounds, increasing the risk of a wide range of health effects. Studies of the environmental fate and human health effects of arsenic require authentic arsenic compounds. We summarize here the synthesis and characterization of more than a dozen methylated and thiolated arsenic compounds that are not commercially available. We discuss the methods of synthesis for the following14 trivalent(Ⅲ) and pentavalent() arsenic compounds: monomethylarsonous acid(MMA~Ⅲ), dicysteinylmethyldithioarsenite(MMA~Ⅲ(Cys)_2), monomethylarsonic acid(MMA~Ⅴ),monomethylmonothioarsonic acid(MMMTAⅤ) or monothio-MMA~Ⅴ, monomethyldithioarsonic acid(MMDTA~Ⅴ) or dithio-MMA~Ⅴ, monomethyltrithioarsonate(MMTTA~Ⅴ) or trithio-MMA~Ⅴ,dimethylarsinous acid(DMA~Ⅲ), dimethylarsino-glutathione(DMA~Ⅲ(SG)), dimethylarsinic acid(DMA~Ⅴ), dimethylmonothioarsinic acid(DMMTA~Ⅴ) or monothio-DMAⅤ, dimethyldithioarsinic acid(DMDTA~Ⅴ) or dithio-DMA~Ⅴ, trimethylarsine oxide(TMAO~Ⅴ), arsenobetaine(AsB), and an arsenicin-A model compound. We have reviewed and compared the available methods,synthesized the arsenic compounds in our laboratories, and provided characterization information. On the basis of reaction yield, ease of synthesis and purification of product, safety considerations, and our experience, we recommend a method for the synthesis of each of these arsenic compounds.     

High-recycled-content hydraulic cements of alternative chemistry for concrete production

Sustainable hydraulic cements based on alkali aluminosilicate chemistry were developed with market-limited wastes acting as the primary aluminosilicate precursors. Two sets of formulations were developed with waste brick or impounded coal ash used at relatively large volume as aluminosilicate precursors. Supplementary materials were used to produce raw materials of viable chemistry. Blends of raw materials were transformed into hydraulic cements by input of mechanical energy without resorting to elevated temperatures. The resultant hydraulic cements exhibited viable strength development characteristics. FTIR, SEM, EDS and NMR analyses were conducted in order to gain insight into the structure of the hydraulic cements and their hydration products. The results pointed at the prevalence of calcium aluminosilicate hydrates among the products of hydration which thoroughly bound the non-hydrated cores of cement particles.     

Aluminium: The Need for a Re-Evaluation of Its Toxicity and Solubility in Mature Forest Stands

Aluminium (Al) is a key element in critical loadcalculations for forest. Here, we argue for re-evaluating theimportance of Al. Effects of two levels of enhanced Alconcentrations and lowered Ca:Al ratios in the soil solutionin a field manipulation experiment in a mature spruce stand(1996–1999) on tree vitality parameters were tested. Inaddition, Al solubility controls were tested. Various loads ofAl were added to forest plots by means of an irrigationsystem. Potentially toxic Al concentrations and criticalratios of Ca to inorganic Al were established. The ratio of Cato total Al was not a suitable indicator for unfavourableconditions for plant growth. No significant effects on crowncondition, tree growth and fine root production were observedafter three years of treatment. In 1999, foliar Mg content inthe highest Al addition treatment had declined significantly.This agreed with the known response to Al stress of seedlingsin nutrient solution experiments. No support was found forusing the chemical criterion Ca:Al ratio in soil solution,foliar and root tissue as an indicator for forest damage dueto acidification. Al solubility was considerably lower thanimplied by the assumption of equilibrium with gibbsite,particularly in the root zone. The gibbsite equilibrium iscommonly used in critical load models. Substitution of thegibbsite equilibrium with an Al-organic matter complexationmodel to describe Al solubility in soil water may have largeconsequences for calculation of critical loads. The resultsindicate that critical load maps for forests should bereconsidered.     

多环芳烃光解活性的量子化学研究

应用量子化学从头算HF／6-311 G(d)和B3LYP／6-311 G(d)方法计算了16种PAHs的多种量子化学参数,选取六种参数为分子结构的描述符,采用最小二乘法对16种PAHs的光解半衰期进行逐步多元线性回归分析,得到两个PAHs光解半衰期的QSAR模型,模型具有较高的相关系数,可有效地用于预测PAHs的光解半衰期,结果表明,HF方法所得模型优于B3LYP方法所得的模型,所得模型与基于半经验PM3算法的QSAR模型相比较,HF从头算方法所建立的QSAR模型比半经验PM3算法的结果要好,在所考查的诸多参数中,分子最高占有轨道特征值EHOMO对PAHs光解半衰期起着决定作用,最后,运用所得模型预测了3种PAHs的光解半衰期。