Speciation and Seasonal Variations of Dissolved Inorganic Arsenic in Jiaozhou Bay,North China

The distributions and biogeochemical cycles of arsenic in the aquatic environment have captured the interest of geochemists due to arsenic’s multiple chemical forms, the toxicity of certain arsenic species and large anthropogenic input. Seasonal variations in the dissolved inorganic arsenic concentration and speciation in Jiaozhou Bay, which is located on the west coast of the Yellow Sea in northern China, are presented here. Three cruises were carried out in Jiaozhou Bay under varying tidal regimes, one at neap tide and one at spring tide in August and one at spring tide in October of 2001. In addition to the transect surveys, the main sources of dissolved inorganic arsenate and arsenite in Jiaozhou Bay, including riverine input from five major tributary rivers, atmospheric dry and wet depositions, and groundwater and wastewater input, were collected in different seasons to estimate arsenic transport through different sources. The mean concentrations of total dissolved inorganic arsenic (TDIAs, As (V+III)) in Jiaozhou Bay were statistically comparable between summer and autumn, with higher concentrations at the northwest and northeast parts of the bay, reflecting human activities. The As (III)/TDIAs ratio ranged between 0.045 and 0.68, with an average of 0.16, implying that arsenate was the dominating species in Jiaozhou Bay. A preliminary box model was established to estimate the water-mass balance and arsenic budgets for Jiaozhou Bay, which demonstrated that river inputs and atmospheric depositions were the main sources of arsenic into Jiaozhou Bay. The concentrations of dissolved inorganic arsenic in Jiaozhou Bay have decreased in the last two decades. Compared with other areas in the world, the concentration of arsenic in Jiaozhou Bay remains at the natural level and this region can be characterized as a less disturbed area.     

Nutrient Dynamics in Jiaozhou Bay

Three cruises were carried out in Jiaozhou Bay (JZB) in the neap tide in October 2002 (fall) and in both neap and spring tides in May 2003 (spring) to understand the relative importance of external nutrient inputs versus physical transport and internal biogeochemical processes. Nutrients (, , , , silicic acid, total dissolved nitrogen (TDN) and phosphorus (TDP), dissolved organic nitrogen (DON) and phosphorus (DOP)) were measured. The concentrations of nutrients were higher in the northern part than in the southern part. High concentrations of and DON in JZB demonstrated the anthropogenic input. Ambient nutrient ratios indicated that the potential limiting nutrients for phytoplankton growth were silicon, and then phosphorus. Nutrients showed an obvious tidal effect with low values at flood tide and high values at ebb tide. Nutrient elements were transported into JZB in the north and output in the south (i.e., into the Yellow Sea), which varied with season, tidal cycle and investigation sites. Water exchange between JZB and the Yellow Sea exports , and DON out of JZB, while it inputs , silicic acid and DOP into JZB. Nutrient budgets demonstrate that riverine input and wastewater discharge are major sources of nutrients, while residual flow is of minor importance in JZB ecosystem. JZB is a sink for the nutrient elements we studied except for DON. Stoichiometric calculations demonstrate that JZB is a net autotrophic system.     

Bench‐ and pilot‐scale applications of electrochemical peroxidation: A new remedial concept

Electrochemical peroxidation (ECP) is a proprietary process that utilizes sacrificial iron electrodes and stochiometrically balanced applications of hydrogen peroxide to efficiently destroy aqueous phase contaminants. In laboratory trials it has been successful in reducing, often to non‐detectable levels, BTEX, fuel additives, chlorinated solvents, and polychlorinated biphenyls in ground waters. The process has also been found effective in reducing the chemical and biological oxygen demand of industrial waste water. Agency‐approved pilot tests will be conducted at two gasoline spill sites during 2000 where traditional pump and treat methods have proven ineffectual because of ground water chemistry or subsurface hydrologic conditions. The ECP process utilizes a tripartite treatment strategy consisting of 1) ex situ chemical oxidation; 2) in situ oxidation by reinjection of treated water with residual oxidants at the head of the plume; and 3) reestablishment of aerobic biodegradation by alteration of subsurface redox conditions. In contrast to other in situ oxidation treatment methods, dissolved iron is derived electrochemically, negating the need for ferrous salt addition. Dilute hydrogen peroxide (3 percent) is incrementally added to maximize oxidation efficiency and eliminate safety and environmental concerns accompanying the use of highly concentrated solutions. Results of laboratory trials and the geological and geochemical considerations of upcoming pilot‐scale applications are presented. Other potential applications currently under investigation include combination with other remedial processes (e.g. permeable barriers and hydrogen release compounds) to insure complete and rapid contaminant mineralization.     

Distributions,Land-source Input and Atmospheric Fluxes of Methane in Jiaozhou Bay

CH₄ concentrations in both the surface and bottom waters of Jiaozhou Bay were determined during four surveys in 2003, which showed variability with both seasons and tidal cycles. Atmospheric fluxes of CH₄ in Jiaozhou Bay showed obvious seasonal and spatial variations, with the highest values occurring in summer and the lowest in winter. The annual emission of CH₄ from Jiaozhou Bay was estimated to be . CH₄ in the water column of Jiaozhou Bay was found to come from several land-sources including riverine water input, sewage water input and groundwater input. The spatial and temporal variation in distributions and atmospheric fluxes of CH₄ in Jiaozhou Bay was influenced mainly by the input of polluted river waters and the sewage effluents along the eastern coast, which highlights the effects of human impacts on CH₄ emission rates.     

A Simplified Model for Predicting the Pollution Exchange Coefficient of Small Tidal Embayments

In recent years there has been a significant increase in the development and application of ever more sophisticated multi-dimensional models for solving the hydrodynamic and constituent transport equations which govern the flushing of pollution. However, advanced numerical modelling techniques can sometimes be augmented by alternative mathematical approaches which use simplified analytical solutions to predict the dispersion of contaminants. In the present article, a novel analytical tidal prism model is described for predicting the pollution flushing characteristics of small tidal embayments. The model relates the water quality response of the basin to the external forcing effects of the tide, the initial pollutant loading and the freshwater inflow rate. In general, the pollution flushing not only depends upon the geometry of the embayment and the tidal range but also on the proportion of effluent water which leaves the basin on an ebb tide, mixes with the surrounding coastal water and returns on subsequent flood tides. This effect has been taken into account in the mathematical model by the inclusion of a ‘pollution-return’ parameter. The analytical approach offers a viable and computationally inexpensive alternative to conventional multi-dimensional pollutant transport simulations and, more importantly, provides an increased understanding of the flushing characteristics of semi-enclosed tidal basins. The efficiency of the tidal flushing can be expressed in terms of the pollution exchange coefficient which measures the proportion of water exchanged with the sea each tidal cycle. To demonstrate the accuracy of the proposed mathematical formulation, analytical water quality predictions are compared against experimental pollution data from a 1:400 scale laboratory model of a generic square harbour. The results demonstrate that the analytical approach provides a simple and robust method of determining the water quality response of well-mixed tidal embayments.     

Evolution of unsaturated hydraulic properties of municipal solid waste with landfill depth and age

Successful modeling of liquid and air flow and hence designing of liquid and air addition systems in the landfills are constrained by the lack of key parameters of unsaturated hydraulic properties of municipal solid waste (MSW), which are strongly dependent on the depth of burial and the degree of decomposition. In this study, water retention curves (WRC) of MSW are measured using pressure plate method on samples repacked according to the in situ unit weight measured during borehole sampling, representing the MSW in shallow, middle, and deep layers. The measured WRC of MSW is well-reproduced by the van Genuchten-Mualem model, and is used to predict the unsaturated hydraulic properties of MSW, including water retention characteristics and unsaturated hydraulic conductivity. The estimated model parameters are consistent with other studies, suggesting that the pressure plate method yields reproducible results. As the landfill depth and age increase, the overburden pressure, the highly decomposed organic matter and finer pore space increase, hence the capillary pressure increases, causing increases in air-entry values, field capacity and residual water content, and decreases in steepness of WRC and saturated water content. The unsaturated hydraulic properties of MSW undergo changes with landfill depth and age, showing more silt loam-like properties as the landfill age increases.     

Evaluation of the effects of PFAS soil adsorption and transformation in the presence of divalent cations under ambient conditions

A bench‐scale study was conducted to evaluate the effect of divalent cations on the adsorption of perfluoroalkyl and polyfluoroalkyl substances (PFAS) onto soil particles. The study entailed batch testing of a synthetic soil mixture under a range of Epsom salt (soluble magnesium sulfate heptahydrate) concentrations. The synthetic soil was produced using a mix of sand, silt, clay, and organic matter that then was mixed and saturated with water collected from a PFAS‐impacted water source. The results indicate that variable concentrations of magnesium (divalent cation) had a minor effect on the sorption of perfluorooctane sulfonate with the highest sorption occurring in the strongest solution of Epsom salt. An unanticipated result of the test involved apparent biomediated transformation of polyfluorinated alkylated sulfonates (fluorotelomers or FTS) to perfluorooctanoic acid, perfluoroheptanoic acid (PFHpA), and perfluorononanoic acid. We believe this is the first time the complete transformation of 6:2 FTS to PFHpA has been observed and reported under ambient surface water‐like conditions within 6 months, a relatively short timeframe.     

Composition and Toxicity of Residual Bunker C Fuel Oil in Intertidal Sediments After 30 Years

In 1970, approximately 2000 m³ of Bunker C crude oil impacted 300 km of Nova Scotia’s coastline following the grounding of the tanker Arrow. Only 10% of the contaminated coast was subjected to cleanup, the remainder was left to cleanse naturally. To determine the long-term environmental impact of residual oil from this spill event, samples of sediment and interstitial water were recovered in 1993, 1997 and 2000 from a sheltered lagoon in Black Duck Cove. This heavily oiled site was intentionally left to recover on its own. Visual observations and chemical analysis confirmed that substantial quantities of the weathered cargo oil were still present within the sediments at this site. However, direct observations of benthic invertebrate abundance suggest that natural processes have reduced the impacts of the residual oil. To confirm this hypothesis, sediment and interstitial water samples from Black Duck Cove were assessed with a comprehensive set of biotests and chemical assays.Residual oil in the sediments had limited effect on hepatic CYP1A protein levels and mixed function oxygenase (MFO) induction in winter flounder (Pleuronectes americanus). No toxicity was detected with the Microtox solid phase test (Vibrio fischeri). Significant sediment toxicity was detected by the amphipod survival test (Eohaustorius estuarius) in four out of the eight contaminated sediments. Interstitial water samples were deemed non-toxic by the Microtox 100% test (Vibrio fischeri) and the echinoid fertilization test (Lytechinus pictus). Sediment elutriates were also found to be non-toxic in the grass shrimp embryo-larval toxicity (GSELTOX) test (Palaemonetes pugio).Recovery at this contaminated site is attributed to natural processes that mediated biodegradation and physical removal of oil from the sediments. In support of the latter mechanism, mineralization experiments showed that all test sediments had the capacity for hexadecane, octacosane and naphthalene degradation, while chemical analysis confirmed that the Bunker C oil from the Arrow had undergone substantial biodegradation.     

Aerosol Composition Change due to Dust Storm: Measurements between 1992 and 1999 at Gosan,Korea

Aerosol composition change between dust storm and non duststorm periods is studied using the TSP (Total SuspendedParticulate) data measured at Gosan, Korea between 1992 and1999. The concentrations of elements measured between 1993and 1996 and those of ions between 1992 and 1999 duringdust storms are compared with those during non-dust stormperiods in spring (March, April, and May). Among theanalyzed ions, the concentrations of crustal species(potassium, calcium, magnesium, and chloride) andanthropogenic species (nitrate and non-sea salt (nss)-sulfate) increased when dust storm occurs while those ofammonium and sodium did not increase. Among the analyzedelements, the concentrations of crustal species (Fe, Al,Ca, Ti, and Zn) increased when dust storm occurs whilethose of anthropogenic species (Mn, V, Ni, Cu, Cd, and Cr)did not increase. The only anthropogenic element of whichconcentration increased during dust storm periods was Pb.It was found that the concentrations of nitrate and nss-sulfatewere highest during spring. Also, the ratio of theyearly average concentrations of nitrate to nss-sulfateincreases, probably due to the emission trend change innortheast Asia, especially, in China.     

铝盐混凝法去除氟离子的一般作用规律

通过混凝除氟、絮体氟吸附和释放等试验考察了铝盐混凝除氟的作用特,探讨了除氟随铝盐投加量、混凝pH等操作参数及铝盐混凝剂本身形态不同时的变化规律。结果表明,铝盐混凝除氟效果与混凝pH密切相关,在pHo 5.8-7.0条件下除氟效果最佳;在相同投加量和各自的最佳混凝条件下,单体铝盐的除氟效果好于聚合铝盐,但其絮体的持氟性能不及聚合铝盐。     

Environmental Sensitivity of a Tropical Coastline (Trinidad,West Indies) to Oil Spills

In the wider Caribbean region, Trinidad has been classified as a high risk area for oil spills by the Intergovernmental Marine Consultative Organization. In order to develop an oil spill environmental sensitivity index, the intertidal zones of fifteen representative coastal sites were monitored for physical and biological parameters during the dry and wet seasons. On a scale of 1–10, sheltered habitats with high productivity are the most sensitive to spilt oil with an index value of 10. Exposed habitats with low productivity are the least sensitive with a value of 1. The index applied to coastal habitats in Trinidad is as follows: mangrove swamps (10), coral-algal reefs (9), sheltered rocky coasts (8), sheltered tidal flats (7), mixed sand and gravel beaches (6), sheltered fine to medium-grained sand beaches (5), exposed rocky shores (4), exposed tidal flats (3), exposed medium to coarse-grained sand beaches (2) and eroding wavecut platforms (1). This study demonstrates an approach to effectively combine biological and physical parameters into a single environmental sensitivity index to oil spills.     

Recovery of high purity zinc from filter ash produced during the thermal treatment of waste and inerting of residual materials.

The method described below recovers zinc, a valuable metal that is present in high concentrations in filter ash from the thermal treatment of waste, and returns the filter ash stripped of heavy metals to the combustion process in order to destroy organic substances. On an industrial scale, the heavy metals in the filter ash were mobilized by means of hydrochloric acid in the acidic fluids produced in the flue-gas scrubbing process without the addition of further chemicals. A pilot plant for implementing the selective reactive extraction (SRE) method on the ash extracts, using a highly selective complexant, was operated over a period of several months in order to obtain a concentrated, high-purity zinc salt solution (mono metal solution). A zinc depletion rate of 99.8% in the aqueous extract was achieved using mixer-settler units. The residual zinc concentration in the waste water was then < 2 mg L(-1). By stripping the loaded organic phase, a concentrated, high-purity mono metal solution with 190 g L(-1) zinc was obtained. Zinc metal with a purity > 99.99% is then separated by means of electrolysis. To destroy organic substances present in the filter ash, particularly dioxins and furans, the extracted filter ash cake was returned to the combustion process together with household waste. Plant operation, raw and pure gas parameters, and quality of the bottom ash produced were not impacted by such recirculation. The profitability of the overall process is attributable both to the recovery of valuable zinc metal and to the cost savings made in waste water treatment and in the disposal of the waste combustion residues because the remaining mixture of filter ash and bottom ash can be reused in a combined form. This method therefore supports the sustainable and economically viable reuse of filter ash.     

钙法提钒尾渣的浮选脱硫试验

根据钙法提钒尾渣的矿物特性,采用浮选法分离其中的石膏以实现脱硫,分别考察了矿浆pH、矿浆液固比、捕收剂添加量及浮选中水循环次数等因素对浮选指标的影响,并进行了理论分析,确定了钙法提钒尾渣浮选脱硫的优选工艺参数.试验结果表明,在矿浆pH为7、矿浆液固比为5:1、捕收剂添加量为0.6～0.8 kg/t的条件下,可获得w(S...     

Effect of composting process on phytotoxicity and speciation of copper, zinc and lead in sewage sludge and swine manure

The concentration and bioavailability of heavy metals in composted organic wastes have negative environmental impacts following land application. Aerobic composting procedures were conducted to investigate the influences of selected parameters on heavy metal speciation and phytotoxicity. Results showed that both of sewage sludge (SSC) and swine manure (SMC) composting systems decreased the pH, the content of organic matter (OM) and dissolved organic carbon (DOC), and total amounts of Cu, Zn and Pb. Sequential extraction showed that readily extractible fractions of exchangeable and carbonate in Cu and Zn increased during SSC composting but decreased during SMC composting, thus their bioavailability factors (BF) enhanced in SSC but declined in SMC. The fraction of reducible iron and manganese (FeMnOX) of Cu and Zn in SSC and FeMnOX-Cu in SMC decreased, but FeMnOX-Zn in SMC gradually increased in the process of compost. In contrast, the changes of Pb distributions were similar in two organic wastes. Pb was preferentially bound to the residual fraction and its BF decreased. The evolution of heavy metal distributions and BF depended on not only total metal concentrations but also the other properties, such as pH, decomposition of OM and decline of DOC. The germination rate (RSG), root growth (RRG) and germination index (GI) of pakchoi (Brassica Chinensis L.) increased during the composting process. Linear regression analysis demonstrated that GI, which could represent phytotoxic behavior to the plants, could be poorly predicted by BF or total amount of metals, i.e., BF-Zn, T-Cu. However, the inclusion of other physicochemical parameters (pH, OM and DOC) could enhance the linear regression significances (R).     

A Preliminary Laboratory Study of Initial Copper Release from Dredge Residuals

A preliminary laboratory study was conducted to investigate the impact of different residual types and sediment surface roughness on copper contaminant fluxes to the water column. Sediments from Torch Lake, Michigan served as the test samples. These sediments are mining by‐products with elevated Cu levels. Six experiments were run during which the sediments were conditioned to simulate different forms of residuals. During these experiments, the water column above the sediments was circulated via peristaltic pumping or orbital shaking and the total and dissolved Cu levels were monitored periodically for 15 days. Dissolved Cu levels indicated that during the first 48 hr the water column concentrations approached equilibrium for all six cases. Total Cu levels increased with time and did reach equilibrium but were more susceptible to fluctuations in water column suspended solids levels. Analysis of the resulting dissolved Cu data indicated that the resulting water column Cu concentrations differed with sediment surface and residual type. The highest dissolved Cu water column concentrations were observed for a roughened surface with a larger surface area. The lowest water column dissolved Cu levels were observed for the case with sediment slurry placed over clean sand. The dissolved Cu levels in the water column for all six simulated conditions were several orders higher than the USEPA ambient water quality criteria for protection of aquatic life. © 2014 Wiley Periodicals, Inc.*     

Anaerobic microbial degradation of poly (3-hydroxyalkanoates) with various terminal electron acceptors

The microbial degradation of poly (3-hydroxyalkanoates) (PHAs) under anaerobic conditions with various terminal electron acceptors was examined. Nitrate-reducing consortia were established using activated sludge, and PHAs were shown to be biodegradable under these conditions. A positive correlation between carbon dioxide production and nitrate reduction was demonstrated. Nitrous oxide accumulated as the main N-containing product of nitrate reduction. The amount of PHAs in activated sludge cultures decreased approximately 20% within 40 days of incubation. Attempts were made to establish iron- and sulfate-reducing consortia from spring water, yet it could not be demonstrated that the mixed cultures were capable of degrading PHAs. Pure cultures of iron- and sulfate-reducing bacteria could not utilize PHAs as sole carbon sources. Methanogenic environments sampled included pond sediment and rumen fluid. PHAs were fermented to methane and carbon dioxide after 10 weeks by a sediment consortium, with 43 to 57% of the substrate carbon transformed to methane. Although it could not be demonstrated that PHAs were biodegraded by a rumen fluid consortium, a facultative anaerobic bacterium, identified as aStaphylococcus sp., that could grow on PHAs was isolated from rumen fluid.     

New Numerical Model Study on a Tidal Flat System – Seasonal,Daily and Tidal Variations

We developed a new numerical model to investigate the dynamics of tidal flat ecosystems and their role in water quality in terms of the carbon cycle. This model was applied to Isshiki, a natural tidal flat area, which is the largest in Mikawa Bay, Japan.This model dealt with variations of biochemical or physical interaction among dissolved oxygen and C–N–P species (comprised of carbon, nitrogen, and phosphorus elements) both on a short-time scale (<24 h) as well as over a long-time scale (seasonal variation). The model indicated that the time dependence on phytoplankton, NH₄–N, NO_x–N, and PO₄–P are more sensitive to daily environmental variation than to seasonal environmental variation. This means that the rotation speed of these materials in the tidal flat area is fast. Here, we defined the rotation speed as the ratio of total fluxes of substance to the mass of the substance. Phytoplankton with a high rotation speed in the tidal flat area means that the tidal flat has the potential to recover from rapidly increasing phytoplankton: red tide. The model also indicated that the peculiar feature of the tidal flat is the mineralization of organic material. The effect on a long term base, is that it prevents the accumulation of sediment, which results in controlling the increase of oxygen consumption in benthic system, which is the cause of oxygen depleted water.     

Novel pilot-scale washing process and equipment for removing Cr(VI) from contaminated soil

In this study, a novel horizontal rotating soil washing process and equipment were developed and tested for pilot-scale remediation of soils from a site polluted by chromium ore process residue. Operating parameters, including cylinder rotational velocity, cylinder tilt angle, heating temperature and liquid/soil ratio, were investigated. The Taguchi method was used for the experiment design, and the standard L16 orthogonal array with four parameters and four levels was selected for optimising the operating parameters. Optimal removal efficiency was achieved at cylinder rotational velocity of 2.5 rpm, cylinder tilt angle of 2.6°, heating temperature of 200 °C and liquid/soil ratio of 8. The efficiency of citric acid as an extractant in the novel process was compared with that of water. The analysis of the residual Cr(VI) concentration of the soil shows that citric acid could efficiently remove 22.89 % more Cr(VI) than water in one-stage washing. The residual Cr(VI) concentration in the soil after the three-stage washing is as low as 26.16 mg/kg, which meets the screening levels for soil environmental risk assessment of sites in Beijing City (30 mg/kg). Further study is currently underway to optimise the novel process and equipment for commercial-scale use.     

分级喷水增湿对半干法烟气脱硫效率的影响

研究了增湿水量、增湿水级数以及增湿水分配方式等参数对半干法烟气脱硫效率的影响。得出了一定试验条件下这些参数的优化值，它们分别为：增湿水量30％、三级增湿、递减分配方式。在此优化工况下，可以使塔内和系统脱硫效率分别达到68％和90％以上，比无增湿时分别提高6％和5％左右。     

Oxygen and Water Barrier Properties of Coated Whey Protein and Chitosan Films

Films of whey protein and chitosan acetic acid salt have lower oxygen permeability than, for example, ethylene-co-vinylalcohol under dry conditions, but water and water vapor seriously impair the gas barrier properties. To reduce the oxygen permeability at 90% relative humidity and the water-vapor transmission rate at 100% relative humidity, the films were coated with an alkyd, a beeswax compound, or a nitrocellulose lacquer. Permeability and transmission rate measurements were performed in accordance with standard methods and showed that the beeswax compound and the nitrocellulose were appropriate as water-vapor barriers. Overall migration to water was measured after 10 days exposure time, with the coated surface exposed to the water, showing that the alkyd-coated and the nitrocellulose-coated films were both below the safety limit for food contact. Water absorbency tests, performed by the Cobb method, showed that the films coated with the beeswax compound or with nitrocellulose lacquer exhibit lower absorbency than the alkyd-coated films.