Photolytic degradation of decabromodiphenyl ethane (DBDPE)

The photolytic degradation of decabromodiphenyl ethane (DBDPE), an alternative flame retardant to decabromodiphenyl ether, was investigated in a variety of matrixes (n-hexane, tetrahydrofuran, methanol/water, humic acid/water, and silica gel) by irradiation under ultraviolet light and in n-hexane under natural light. Photolytic degradation of DBDPE occurs in all the matrixes investigated within the irradiation period (<320 min). The degradation experiments showed varied reaction rates, dependent on the matrixes, with increasing half-lives (t_1/2) in the order of tetrahydrofuran (t_1/2 = 6.0 min) > n-hexane (t_1/2 = 16.6 min) > humic acid/water (30 < t_1/2 < 60) > silica gel (t_1/2 = 75.9 min) > methanol/water (t_1/2 > 240 min). The reaction in tetrahydrofuran, n-hexane, and silica gel matrixes can be described by the pseudo first order kinetics. Nevertheless, the matrixes have little effect on the degradation product distributions of DBDPE. A numbers of debrominated intermediates were identified. The degradation involves the initial formation of nona-BDPEs and the subsequent decomposition of these congeners to lower brominated congeners (octa- and hepta-BDPEs) within the irradiation time. To our knowledge, the present work is the first attempt to investigate the photolytic degradation kinetics and the identification of intermediates, as well as the degradation mechanism, during the degradation of DBDPE. Further research is needed to understand the photolytic degradation pattern of DBDPE in the natural environment.     

Integrated risk assessment framework for transformation products of emerging contaminants: what we know and what we should know

● A better risk assessment can combine the improved non-target analysis method. ● Multi-evidence is advised in molecular determination and risk-based prioritization. ● Combining omics, multi-endpoint EDA, and machine learning to assess product risks. The continuous input of various emerging contaminants (ECs) has inevitably introduced large amounts of transformation products (TPs) in natural and engineering water scenarios. Structurally similar to the precursor species, the TPs are expected to possess comparative, if not more serious, environmental properties and risks. This review summarizes the state-of-the-art knowledge regarding the integrated risk assessment frameworks of TPs of ECs, mainly involving the exposure- and effect-driven analysis. The inadequate information within existing frameworks that was essential and critical for developing a better risk assessment framework was discussed. The main strategic improvements include (1) non-targeted product analysis in both laboratory and field samples, (2) omics-based high-throughput toxicity assessment, (3) multichannel-driven mode of action in conjugation with effect-directed analysis, and (4) machine learning technology. Overall, this review provides a concise but comprehensive insight into the optimized strategy for evaluating the environmental risks and screening the key toxic products from the cocktail mixtures of ECs and their TPs in the global water cycle. This facilitates deciphering the mode of toxicity in complex chemical mixtures and prioritizing the regulated TPs among the unknown products, which have the potential to be considered a class of novel “ECs” of great concern.     

Tipping Toward Sustainability: Emerging Pathways of Transformation

This article explores the links between agency, institutions, and innovation in navigating shifts and large-scale transformations toward global sustainability. Our central question is whether social and technical innovations can reverse the trends that are challenging critical thresholds and creating tipping points in the earth system, and if not, what conditions are necessary to escape the current lock-in. Large-scale transformations in information technology, nano- and biotechnology, and new energy systems have the potential to significantly improve our lives; but if, in framing them, our globalized society fails to consider the capacity of the biosphere, there is a risk that unsustainable development pathways may be reinforced. Current institutional arrangements, including the lack of incentives for the private sector to innovate for sustainability, and the lags inherent in the path dependent nature of innovation, contribute to lock-in, as does our incapacity to easily grasp the interactions implicit in complex problems, referred to here as the ingenuity gap. Nonetheless, promising social and technical innovations with potential to change unsustainable trajectories need to be nurtured and connected to broad institutional resources and responses. In parallel, institutional entrepreneurs can work to reduce the resilience of dominant institutional systems and position viable shadow alternatives and niche regimes.     

Stability of Fe–As composites formed with As(V) and aged ferrihydrite

During the aging process, ferrihydrite was transformed into mineral mixtures composed of different proportions of ferrihydrite, goethite, lepidocrocite and hematite. Such a transformation may affect the fixed ability of arsenic. In this study, the stability of Fe-As composites formed with As(V) and the minerals aged for 0, 1, 4, 10 and 30 days of ferrihydrite were systematically examined, and the effects of molar of ratios Fe/As were also clarified using kinetic methods combined with multiple spectroscopic techniques. The results indicated that As(V) was rapidly adsorbed on minerals during the initial polymerization process, which delayed both the ferrihydrite conversion and the hematite formation. When the Fe/As molar ratio was 1.875 and 5.66, the As(V) adsorbed by ferrihydrite began to release after 6 hr and 12 hr, respectively. The corresponding release amounts of As(V) were 0.55 g/L and 0.07 g/L, and the adsorption rates were 92.43% and 97.50% at 60 days, respectively. However, the As(V) adsorbed by the transformation products aged for 30 days of ferrihydrite began to release after adsorbed 30 days. The corresponding release amounts of As(V) were 0.25 g/L and 0.03 g/L, and the adsorption rates were 84.23% and 92.18% after adsorbed 60 days, for the Fe/As=1.875 and 5.66, respectively. Overall, the combination of As(V) with ferrihydrite and aged products transformed from a thermodynamically metastable phase to a dynamically stable state within a certain duration. Moreover, the aging process of ferrihydrite reduced the sorption ability of arsenate by iron (hydr)oxide but enhanced the stability of the Fe-As composites.     

Anaerobic testosterone degradation in Steroidobacter denitrificans - Identification of transformation products

The transformation of the androgenic steroid testosterone by gammaproteobacterium Steroidobacter denitrificans was studied under denitrifying conditions. For the first time, growth experiments showed that testosterone was mineralized under consumption of nitrate and concurrent biomass production. Experiments with cell suspensions using [4-¹⁴C]-testosterone revealed the intermediate production of several transformation products (TPs). Characterisation of ten TPs was carried out by means of HPLC coupled to high resolution mass spectrometry with atmospheric pressure chemical ionization as well as ¹H and ¹³C NMR spectroscopy. 3β-hydroxy-5α-androstan-17-one (trans-androsterone) was formed in the highest amount followed by 5α-androstan-3,17-dione. The data suggests that several dehydrogenation and hydrogenation processes take place concurrently in ring A and D because no consistent time-resolved pattern of TP peaks was observed and assays using 2 TPs as substrates resulted in essentially the same TPs. The further transformation of testosterone in S. denitrificans seems to be very efficient and fast without formation of detectable intermediates.     

Fe(II)-mediated transformation of schwertmannite associated with calcium from acid mine drainage treatment

Schwertmannite is an important Fe(III)-oxyhydroxysulfate in acid mine drainage (AMD) polluted areas and its stability depends on surrounding environmental factors and previously bound elements. The treatment and neutralization of AMD normally involve the use of lime, which leads to the discharge of abundant Ca in the mining area. Such an environmental disturbance brings up an important and less considered problem of how the reductive transformation of schwertmannite associated with coexisting Ca occurred. Here, the Fe(II)-mediated transformation of Ca-adsorbed schwertmannite and subsequent Ca repartitioning behaviors were investigated. Results showed that adsorbed Ca had a weak inhibitory effect on Fe(II)-mediated schwertmannite transformation. Release of SO₄²⁻ and SEM images both indicated that transformation rates of schwertmannite decreased under the influence of adsorbed Ca. XRD patterns indicated that adsorbed Ca altered schwertmannite transformation pathways and product compositions upon treatment with 0.4 mmol/L Fe(II). The end products of Sch notably contained both goethite and lepidocrocite; however, transformation products of SchCa only contained goethite all along. Approximately 33.5% of the surface adsorbed-Ca was released into solution within 6 hr after Fe(II) injection. Aqueous Ca behaved in a “first release and then im-mobilization” manner, which indicated dissolution and secondary mineralization drove Ca migration during the Fe(II)-mediated transformation of SchCa. Adsorbed Ca blocked the surface sites for subsequent Fe(II) adsorption, limited the Fe(II)-Fe(III) ETAE, and decreased the transformation rates. This work sheds light on the complex geochemical behavior of schwertmannite under the influences of environmental perturbations in AMD environments.     

Rural vulnerability to environmental change in the irrigated lowlands of Central Asia and options for policy-makers: A review

Climate change, land degradation and drought affect millions of people living in drylands worldwide. With its food security depending almost entirely on irrigated agriculture, Central Asia is one of the arid regions highly vulnerable to water scarcity. Previous research of land and water use in the region has focused on improving water-use efficiency, soil management and identifying technical, institutional and agricultural innovations. However, vulnerability to climate change has rarely been considered, in spite of the imminent risks due to a higher-than-average warming perspective and the predicted melting of glaciers, which will greatly affect the availability of irrigation water. Using the Khorezm region in the irrigated lowlands of northwest Uzbekistan as an example, we identify the local patterns of vulnerability to climate variability and extremes. We look at on-going environmental degradation, water-use inefficiency, and barriers to climate change adaptation and mitigation, and based on an extensive review of research evidence from the region, we present concrete examples of initiatives for building resilience and improving climate risk management. These include improving water use efficiency and changing the cropping patterns that have a high potential to decrease the exposure and sensitivity of rural communities to climate risks. In addition, changes in land use such as the afforestation of degraded croplands, and introducing resource-smart cultivation practices such as conservation agriculture, may strengthen the capacity of farmers and institutions to respond to climate challenges. As these can be out-scaled to similar environments, i.e. the irrigated cotton and wheat growing lowland regions in Central Asia and the Caucasus, these findings may be relevant for regions beyond the immediate geographic area from which it draws its examples.     

Chlorination of para-substituted phenols: Formation of α, β-unsaturated C4-dialdehydes and C4-dicarboxylic acids

Despite the widespread occurrence of phenols in anthropogenic and natural compounds, their fate in reactions with hypochlorous acid (HOCl), one of the most common water treatment disinfectants, remains incompletely understood. To close this knowledge gap, this study investigated the formation of disinfection by-products (DBPs) in the reaction of free chlorine with seven para-substituted phenols. Based on the chemical structures of the DBPs and the reaction mechanisms leading to their formation, the DBPs were categorized into four groups: chlorophenols, coupling products, substituent reaction products, and ring cleavage products. In contrast to previous studies that investigated the formation of early-stage chlorophenols, the primary focus of this study was on the elucidation of novel ring cleavage products, in particular α, β-unsaturated C₄-dialdehydes, and C₄-dicarboxylic acids, which, for the first time, were identified and quantified in this study. The molar yields of 2-butene-1,4-dial (BDA), one of the identified α, β-unsaturated C₄-dialdehydes, varied among the different phenolic compounds, reaching a maximum value of 10.4% for bisphenol S. Molar yields of 2-chloromaleic acid (Cl-MA), one of the identified C₄-dicarboxylic acids, reached a maximum value of 30.5% for 4-hydroxy-phenylacetic acid under given conditions. 2,4,6-trichlorophenol (TCP) was shown to be an important intermediate of the parent phenols and the C₄-ring cleavage products. Based on the temporal trends of α, β-unsaturated C₄-dialdehydes and C₄-dicarboxylic acids, their formation is likely attributable to two separate ring cleavage pathways. Based on the obtained results, an overall transformation pathway for the reaction of para-substituted phenols with free chlorine leading to the formation of novel C₄ ring cleavage products was proposed.     

灾害史研究中的年代换算及其软件

“灾害史中的年代换算（TCHD）”软件是进行年代换算的专用软件。本文研究了几种主要历法的年代换算的具体算法．介绍了该软件的结构，流程和功能．TCHD软件使灾害学和历史学等领域的研究人员摆脱了传统的朔闰表式的历法对照和检索方式，并成为灾害史工作计算机化的一部分。     

氮氧化物生态环境中的转化及危害

在对氮氧化物污染引起奶牛亚硝酸中毒事件的调查基础上，通过室内模拟实验研究氮氧化物的转化过程及测定方法，探讨氮氧化物的生态环境中的转化规律，分析其危害途径和机理，研究表明氮氧化物中的二氧化氮遇水迅速反应生成硝酸和亚硝酸，而对生态环境和人畜产生危害。