Water-soluble matter in PM2.5 in a coastal city over China: Chemical components, optical properties, and source analysis

Although marine and terrestrial emissions simultaneously affect the formation of atmospheric fine particles in coastal areas, knowledge on the optical properties and sources of water-soluble matter in these areas is still scarce. In this work, taking Qingdao, China as a typical coastal location, the chemical composition of PM_2.5 during winter 2019 was analyzed. Excitation-emission matrix fluorescence spectroscopy was combined with parallel factor analysis model to explain the components of water-soluble atmospheric chromophores of PM_2.5. Our analysis indicated that NO₃⁻, NH₄⁺ and SO₄²⁻ ions accounted for 86.80% of the total ion mass, dominated by NO₃⁻. The ratio of [NO₃⁻]/[SO₄²⁻] was up to 2.42 ± 0.84, suggesting that mobile sources play an important role in local pollutants emission. The result of positive correlation between Abs₃₆₅ with K⁺ suggests that biomass burning is an important source of water-soluble organic compounds (WSOC). Six types of fluorophores (C1-C6), all humic-like substances, were identified in WSOC. Humification index, biological index and fluorescence index in winter were 1.66 ± 0.34, 0.51 ± 0.44 and 1.09 ± 0.78, respectively, indicating that WSOC in Qingdao were mainly terrestrial organic matters. Overall, although the study area is close to the ocean, the contribution of terrestrial sources to PM_2.5, especially vehicle exhaust and coal combustion, is still much higher than that of marine sources. Our study provides a more comprehensive understanding of chemical and optical properties of WSOC based on PM_2.5 in coastal areas, and may provide ground for improving local air quality.     

锰氧化物改性生物炭基质材料对典型喹诺酮类抗生素的吸附及其在人工湿地的应用

以废弃花生壳为原料,制备锰氧化物改性生物炭球（MBCB）用于去除水中的环丙沙星（CIP）和恩诺沙星（ENR）,探究MBCB对CIP和ENR的吸附特性及在人工湿地中的应用效果.结果表明,负载锰氧化物的MBCB对CIP和ENR的吸附过程分别符合准一级和准二级动力学模型,混合吸附过程符合准二级动力学模型,Langmuir和Freundlich等温模型都可以较好地拟合MBCB对CIP和ENR的吸附过程,在25℃条件下,通过Langmuir模型拟合出的对CIP和ENR的最大吸附量分别为3.84 mg·g^-1和2.01 mg·g^-1.MBCB对CIP和ENR的吸附过程主要受到内扩散和边界层扩散的控制,是自发的吸热过程,氢键和静电相互作用参与到吸附过程当中.添加MBCB作为基质的人工湿地对CIP和ENR的平均去除率达70.7%和62.9%,分别为对照组的1.625倍和1.719倍.同时,添加MBCB的湿地微生物丰度和多样性所受影响相对较小,这说明MBCB能缓解人工湿地中CIP和ENR的毒性,保证人工湿地对抗生素的去除效果.     

Hydrologic Controls on Nitrogen and Phosphorous Dynamics in Relict Oxbow Wetlands Adjacent to an Urban Restored Stream

Although wetlands are known to be sinks for nitrogen (N) and phosphorus (P), their function in urban watersheds remains unclear. We analyzed water and nitrate (NO₃^?) and phosphate (PO₄^3?) dynamics during precipitation events in two oxbow wetlands that were created during geomorphic stream restoration in Baltimore County, Maryland that varied in the nature and extent of connectivity to the adjacent stream. Oxbow 1 (Ox1) received 1.6‐4.2% and Oxbow 2 (Ox2) received 4.2‐7.4% of cumulative streamflow during storm events from subsurface seepage (Ox1) and surface flow (Ox2). The retention time of incoming stormwater ranged from 0.2 to 6.7 days in Ox1 and 1.8 to 4.3 days in Ox2. Retention rates in the wetlands ranged from 0.25 to 2.74 g N/m²/day in Ox1 and 0.29 to 1.94 g N/m²/day in Ox2. Percent retention of the NO₃^?‐N load that entered the wetlands during the storm events ranged from 64 to 87% and 23 to 26%, in Ox1 and Ox2, respectively. During all four storm events, Ox1 and Ox2 were a small net source of dissolved PO₄^3? to the adjacent stream (i.e., more P exited than entered the wetland), releasing P at a rate of 0.23‐20.83 mg P/m²/day and 3.43‐24.84 mg P/m²/day, respectively. N and P removal efficiency of the oxbows were regulated by hydrologic connectivity, hydraulic loading, and retention time. Incidental oxbow wetlands have potential to receive urban stream and storm flow and to be significant N sinks, but they may be sources of P in urban watersheds.     

Long-Term Relationship between Phosphorus Inputs and Wetland Phosphorus Concentrations in a Northern Everglades Marsh

Assessments of long-term relationships between changes innutrient inputs and wetland nutrient concentrations can becomplicated by fluctuations in other environmental factors aswell as by problems typical of long-term monitoring data.Consequently, statistical analysisof these types of data sets requirescareful consideration of environmental covariates, potentialbiases in the monitoring design, and irregularities caused bychanges in field sampling protocols. We evaluated therelationship between anthropogenic phosphorus (P) inputs andwater-column total P (TP) concentrations in a northernEverglades marsh by statistically analyzing available datacollected from several sampling programs over the past 20 years(1978–1997). Canal inputs of agricultural runoff contributemost of the P to the marsh and have produced a zone ofenrichment within the marsh during the past few decades.Regression analyses showed that both canal and marsh TPconcentrations increased during the 1980s and then decreased inthe 1990s. However, the statistical relationship between canal Pinputs and marsh TP, while significant, generally was weakexcept for marsh locations adjacent to the canal. Strongerrelationships existed between marsh TP and hydrologic parameterssuch as marsh water depth, which is controlled by changes inweather patterns and marsh management. In particular, dryconditions during the 1980s may have contributed to observedincreases in marsh P concentrations and the movement of a P`front' further into the marsh. Higher rainfall and water depthsand agricultural best management programs initiated during the1990s have been associated with reduced P concentrations incanal waters entering the marsh. While it is anticipated thatthis reduction eventually will result in lower marsh TPconcentrations, this effect is not yet evident, possibly due tointernal loading of P from enriched marsh soils. Our findingsillustrate some of the environmental factors that can complicateattempts to develop empirical relationships between P inputs andwetland P concentrations and to use such relationships to forecast changesin marsh concentrations based on past monitoring data alone.     

Forms of Nitrogen (NO 3 - -N; NO 2 - -N and NH 2 CONH 2 -N) and their relations to A.O.U. in the Indian coastal waters of Arabian Sea

The distribution of three important dissolved forms of nitrogen, viz. nitrate, nitrite and urea in the surface and bottom water samples collected from 27 selected hydrographic profiles, in the Arabian Sea, along the west coast of India is described. Of the three forms, nitrate concentrations were the highest and comparatively higher concentrations were observed in the bottom water. Decomposition of organic matter resulting in the release of the thermodynamically stable nitrogen species, i.e. nitrate, may be the major factor resulting in higher nitrate concentrations at these depths, where the water is also characterized by low values of dissolved oxygen and temperature. The significant positive correlation between A.O.U. and nitrate of the bottom water samples emphasizes the role of oxidative decomposition of organic matter which plays an active role in reducing the oxygen concentrations below the theoretical values since at this depth ( , 200 m) the net production is taken to be zero. This is also evidenced by the negative correlation of nitrate with dissolved oxygen and temperature, for the bottom samples.     

Removal of trace elements in three horizontal sub-surface flow constructed wetlands in the Czech Republic

Between March 2006 and June 2008 removal of 34 trace elements was measured on a monthly basis at three horizontal-flow constructed wetlands in the Czech Republic designed to treat municipal wastewater. In general, the results indicated a very wide range of removal efficiencies among studied elements. The highest degree of removal (average of 90%) was found for aluminum. High average removal was also recorded for zinc (78%). Elements removed in the range of 50-75% were uranium, antimony, copper, lead, molybdenum, chromium, barium, iron and gallium. Removal of cadmium, tin, mercury, silver, selenium and nickel varied between 25 and 50%. Low retention (0-25%) was observed for vanadium, lithium, boron, cobalt and strontium. There were two elements (manganese and arsenic) for which average outflow concentrations were higher compared to inflow concentrations. Reduced manganese compounds are very soluble and therefore they are washed out under anaerobic conditions.     

Contaminants in the coastal karst aquifer system along the Caribbean coast of the Yucatan Peninsula, Mexico

Intensive land development as a result of the rapidly growing tourism industry in the “Riviera Maya” region of the Yucatan Peninsula, Mexico may result in contamination of groundwater resources that eventually discharge into Caribbean coastal ecosystems. We deployed two types of passive sampling devices into groundwater flowing through cave systems below two communities to evaluate concentrations of contaminants and to indicate the possible sources. Pharmaceuticals and personal care products accumulated in the samplers could only have originated from domestic sewage. PAHs indicated contamination by runoff from highways and other impermeable surfaces and chlorophenoxy herbicides accumulated in samplers deployed near a golf course indicated that pesticide applications to turf are a source of contamination. Prevention and mitigation measures are needed to ensure that expanding development does not impact the marine environment and human health, thus damaging the tourism-based economy of the region.     

DOC removal paradigms in highly humic aquatic ecosystems

Background, aim, and scope  Dissolved humic substances (HS) usually comprise 50–80% of the dissolved organic carbon (DOC) in aquatic ecosystems. From a trophic and biogeochemical perspective, HS has been considered to be highly refractory and is supposed to accumulate in the water. The upsurge of the microbial loop paradigm and the studies on HS photo-degradation into labile DOC gave rise to the belief that microbial processing of DOC should sustain aquatic food webs in humic waters. However, this has not been extensively supported by the literature, since most HS and their photo-products are often oxidized by microbes through respiration in most nutrient-poor humic waters. Here, we review basic concepts, classical studies, and recent data on bacterial and photo-degradation of DOC, comparing the rates of these processes in highly humic ecosystems and other aquatic ecosystems. Materials and methods  We based our review on classical and recent findings from the fields of biogeochemistry and microbial ecology, highlighting some odd results from highly humic Brazilian tropical lagoons, which can reach up to 160 mg C L⁻¹. Results and discussion  Highly humic tropical lagoons showed proportionally lower bacterial production rates and higher bacterial respiration rates (i.e., lower bacterial growth efficiency) than other lakes. Zooplankton showed similar δ¹³C to microalgae but not to humic DOC in these highly humic lagoons. Thus, the data reviewed here do not support the microbial loop as an efficient matter transfer pathway in highly humic ecosystems, where it is supposed to play its major role. In addition, we found that some tropical humic ecosystems presented the highest potential DOC photo-chemical mineralization (PM) rates reported in the literature, exceeding up to threefold the rates reported for temperate humic ecosystems. We propose that these atypically high PM rates are the result of a joint effect of the seasonal dynamics of allochthonous humic DOC input to these ecosystems and the high sunlight incidence throughout the year. The sunlight action on DOC is positive to microbial consumption in these highly humic lagoons, but little support is given to the enhancement of bacterial growth efficiency, since the labile photo-chemical products are mostly respired by microbes in the nutrient-poor humic waters. Conclusions  HS may be an important source of energy for aquatic bacteria in humic waters, but it is probably not as important as a substrate to bacterial growth and to aquatic food webs, since HS consumption is mostly channeled through microbial respiration. This especially seems to be the case of humic-rich, nutrient-poor ecosystems, where the microbial loop was supposed to play its major role. Highly humic ecosystems also present the highest PM rates reported in the literature. Finally, light and bacteria can cooperate in order to enhance total carbon degradation in highly humic aquatic ecosystems but with limited effects on aquatic food webs. Recommendations and perspectives  More detailed studies using C- and N-stable isotope techniques and modeling approaches are needed to better understand the actual importance of HS to carbon cycling in highly humic waters.     

Pollutants and the health of green sea turtles resident to an urbanized estuary in San Diego, CA

Rapid expansion of coastal anthropogenic development means that critical foraging and developmental habitats often occur near highly polluted and urbanized environments. Although coastal contamination is widespread, the impact this has on long-lived vertebrates like the green turtle (Chelonia mydas) is unclear because traditional experimental methods cannot be applied. We coupled minimally invasive sampling techniques with health assessments to quantify contaminant patterns in a population of green turtles resident to San Diego Bay, CA, a highly urbanized and contaminated estuary. Several chemicals were correlated with turtle size, suggesting possible differences in physiological processes or habitat utilization between life stages. With the exception of mercury, higher concentrations of carapace metals as well as 4,4′-dichlorodiphenyldichloroethylene (DDE) and γ chlordane in blood plasma relative to other sea turtle studies raises important questions about the chemical risks to turtles resident to San Diego Bay. Mercury concentrations exceeded immune function no-effects thresholds and increased carapace metal loads were correlated with higher levels of multiple health markers. These results indicate immunological and physiological effects studies are needed in this population. Our results give insight into the potential conservation risk contaminants pose to sea turtles inhabiting this contaminated coastal habitat, and highlight the need to better manage and mitigate contaminant exposure in San Diego Bay.