Free atmospheric phosphine concentrations and fluxes in different wetland ecosystems, China.

Atmospheric phosphine (PH(3)) fluxes from typical types of wetlands and PH(3) concentrations in adjacent atmospheric air were measured. The seasonal distribution of PH(3) in marsh and paddy fields were observed. Positive PH(3) fluxes are significantly related to high air temperature (summer season) and increased vegetation. It is concluded that vegetation speeds up the liberation of PH(3) from soils, while water coverage might function as a diffusion barrier from soils or sediments to the atmosphere. The concentrations of atmospheric PH(3) (ng m(-3)) above different wetlands decrease in the order of paddy fields (51.8 ± 3.1) > marsh (46.5 ± 20.5) > lake (37.0 ± 22.7) > coastal wetland (1.71 ± 0.73). Highest atmospheric PH(3) levels in marsh are found in summer. In paddy fields, atmospheric PH(3) concentrations in flourishing stages are higher than those in slowly growing stages.

Role of protein, amino acids, and enzyme activity on odor production from anaerobically digested and dewatered biosolids.

The main objective of this research was to test the hypothesis that bioavailable protein and, more specifically, the sulfur-containing amino acids within the protein, can be degraded by proteolytic enzymes to produce odor-causing compounds--mainly volatile sulfur compounds (VSCs)--during biosolids storage. To achieve these objectives, samples of digester effluent and cake solids were collected at 11 different wastewater treatment plants in North America, and the samples were analyzed for protein and amino acid content and general protein-degrading enzyme activity. At the same time, cake samples were stored using headspace bottles, the concentration of VSCs were measured using gas chromatography, and olfactometry measurements were made by a trained odor panel. The results showed that the bound cake protein content and methionine content was well-correlated with VSC production and the detection threshold measured by the odor panel.

Generation pattern of sulfur containing gases from anaerobically digested sludge cakes.

Eleven dewatered sludge cakes collected from anaerobic digesters at different treatment plants were evaluated for the amount, type, and pattern of odorous gas production. All but one of the sludge cakes were from mesophilic anaerobic digesters. One was from a thermophilic digester. The pattern and quantities of sulfur gases were found to be unique for each of the samples with regard to the products produced, magnitude, and subsequent decline. The main odor-causing chemicals were volatile sulfur compounds, which included hydrogen sulfide, methanethiol, and dimethyl sulfide. Volatile sulfur compound production peaked in 3 to 8 days and then declined. The decline was a result of conversion of organic sulfur compounds to sulfide. In one side-by-side test, a high-solids centrifuge cake generated more odorous compounds than the low-solids centrifuge cake. The data show that anaerobic digestion does not eliminate the odor potential of anaerobically digested dewatered cakes.

Cycling of volatile organic sulfur compounds in anaerobically digested biosolids and its implications for odors.

The objectives of this research were to elucidate the mechanisms for production and degradation of volatile organic sulfur compounds (VOSCs), key odor causing compounds produced by biosolids. These compounds included methanethiol (MT), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS). A series of experiments were used to probe various pathways hypothesized to produce and degrade these VOSCs. The production of MT was found to mainly occur from degradation of methionine and the methylation of hydrogen sulfide. DMS was formed through the methylation of MT. DMDS was formed by MT oxidation. All three of the VOSCs were readily degraded by methanogens and a cyclic pathway was proposed to describe the production and degradation of VOSCs. The research demonstrated that the main source of VOSCs was the biodegradation of protein within the biosolids and the results provided a framework for understanding the production of odor from anaerobically digested sludges before and after dewatering.

Dimethyl sulfoxide (DMSO) waste residues and municipal waste water odor by dimethyl sulfide (DMS): the north-east WPCP plant of Philadelphia.

This study shows for the first time that overlooked mg/L concentrations of industrial dimethyl sulfoxide (DMSO) waste residues in sewage can cause "rotten cabbage" odor problems bydimethyl sulfide (DMS) in conventional municipal wastewater treatment. In laboratory studies, incubation of activated sludge with 1-10 mg/L DMSO in bottles produced dimethyl sulfide (DMS) at concentrations that exceeded the odor threshold by approximately 4 orders of magnitude in the headspace gas. Aeration at a rate of 6 m3 air/m3 sludge resulted in emission of the DMS into the exhaust air in a manner analogous to that of an activated sludge aeration tank. A field study atthe NEWPCP sewage treatment plant in Philadelphia found DMSO levels intermittently peaking as high as 2400 mg/L in sewage near an industrial discharger. After 3 h, the DMSO concentration in the influent to the aeration tank rose from a baseline level of less than 0.01 mg/L to a level of 5.6 mg/L and the DMS concentration in the mixed liquor rose from less than 0.01 to 0.2 mg/L. Finding this link between the intermittent occurrence of DMSO residues in influent of the treatment plant and the odorant DMS in the aeration tank was the keyto understanding and eliminating the intermittent "canned corn" or "rotten cabbage" odor emissions from the aeration tank that had randomly plagued this plant and its city neighborhood for two decades. Sewage authorities should consider having wastewater samples analyzed for DMSO and DMS to check for this possible odor problem and to determine whether DMSO emission thresholds should be established to limit odor generation at sewage treatment plants.

Tropospheric phosphine and its sources in coastal antarctica.

Earlier reports show very low concentrations of phosphine in remote air of the lower troposphere of nonpolar regions, in the low ng m(-3) range during the night and in the pg m(-3) range during daylight around noon. In this study, abnormally and unexpectedly high phosphine concentrations (30.0-407.8 ng m(-3), 11 locations) were found in polar air samples collected on Millor Peninsula, eastern Antarctica and Fildes Peninsula, western Antarctica. The maximum concentration was measured in the atmosphere of penguin colonies. Field phosphine emission rates from four colonies were 8.99 ng m(-2) h(-1) (skua colony), 9.56 ng m(-2) h(-1) (gentoo penguin colony), 39.96 ng m-2 h-' (seal colony) and 63.58 ng m(-2) h(-1) (empire penguin colony), respectively. Our air sampling sites are located downwind of two large penguin colonies, indicating that penguin colony emission is the predominant source for atmospheric PH3 on Millor Peninsula. Laboratory scale incubation of ornithogenic soils amended by penguin guanos yielded a maximum PH3 production rate of 0.58 ng kg(-1) d(-1) specifically at low temperature (4 degrees C). Significant concentrations of phosphine occur in the atmosphere of coastal Antarctica and confirm the existence of a small gaseous link in the phosphorus cycle of the Antarctic tundra ecosystem.

Phosphine from rocks: mechanically driven phosphate reduction?

Natural rock and mineral samples released trace amounts of phosphine during dissolution in mineral acid. An order of magnitude more phosphine (average 1982 ng PH3 kg rock and maximum 6673 ng PH3/kg rock) is released from pulverized rock samples (basalt, gneiss, granite, clay, quartzitic pebbles, or marble). Phosphine was correlated to hardness and mechanical pulverization energy of the rocks. The yield of PH3 ranged from 0 to 0.01% of the total P content of the dissolved rock. Strong circumstantial evidence was gathered for reduction of phosphate in the rock via mechanochemical or "tribochemical" weathering at quartz and calcite/marble inclusions. Artificial reproduction of this mechanism by rubbing quartz rods coated with apatite-phosphate to the point of visible triboluminescence, led to detection of more than 70 000 ng/kg PH3 in the apatite. This reaction pathway may be considered a mechano-chemical analogue of phosphate reduction from lightning or electrical discharges and may contribute to phosphine production via tectonic forces and processing of rocks.

Analysis of reduced phosphorus in samples of environmental interest.

The combination of ion chromatography (IC) and inductively coupled plasma emission spectroscopy (ICP-ES) was used forthe sensitive and specific detection of hypophosphite (PO2), phosphite (PO3), methylphosphonic acid (MPA), and phosphate (PO4). Application of this technique to a wide range of environmental samples proved that reduced phosphorus was present in some situations including process water from thermal phosphorus plants, drinking water contacting cast iron, and phosphorus corrosion inhibitor used in water treatment and in sewage wastewater. Preliminary testing did not detect high concentrations of reduced phosphorus and phosphine in situations where it was previously reported to be very important, including anaerobic digesters in wastewater treatment plants. The new IC-ICP-ES technique is a promising tool for use in corrosion and soil research where phosphites are likely to be present.

Effect of pH on phosphine production and the fate of phosphorus during anaerobic process with granular sludge.

The effect of pH on phosphine formation during anaerobic cultivation of granular sludge was investigated. The sludge was taken from full-scale anaerobic reactors treating brewery wastewater. Acetate and phosphate were used as the carbon source and phosphorus source respectively. After 10 days cultivation in the dark, results showed that acidic conditions were more favorable for free phosphine production. At pH 5, the optimum concentration 86.42 ng PH3 m-3 of free phosphine was obtained. The level at pH 7 was reduced to 18.53 ng PH3 m-3, about 1/5 of the maximum. The maximum concentration of matrix-bound phosphine of 3.30 ng PH3 kg-1 wet sludge was achieved at pH 6. More than 83% of the total phosphine was matrix-bound phosphine, which accounted for 0.003-0.009 per thousand of the phosphate removal, while free phosphine comprised 0.00002-0.001 per thousand of the phosphate removal. Most of the phosphorus removal from solution was turned into chemical precipitation or was adsorbed by sludge. The mechanism of the phosphate reduction-step in the formation of phosphine production is still unknown. The promotion of phosphine formation by low pH is compatible with an acidic bio-corrosion mechanism of metal particles in the sludge or of metal phosphides which form phosphine at low pH.

Matrix bound phosphine formation and depletion in eutrophic lake sediment fermentation-simulation of different environmental factors.

Closed anaerobic batch-fermentation of eutrophic lake sediment samples was performed under variation of four environmental fermentation factors (pH, temperature, water/sediment ratio and disturbance) to learn how the quantity of phosphine will change and if the quantity of phosphine can increase. The fermentation conditions where matrix bound phosphine (MBP) increased (doubled from 3193+/-520 to about 7982+/-1003 ng/kg) were: a pH of 8 and of 10 (as compared to 1, 2, 4, 6, 12), a temperature of 20 and 30 degrees C (as compared to 4 and 40 degrees C), a water/sediment ratio of 3:1 (as compared to 1:1, 2:1, 5:1) and a disturbance of 100 r/min (as compared to 0 r/min), respectively. Although, over the full time course of fermentation, the balance of phosphine production became negative again or did remain almost unchanged under most conditions. A pH of 1 or disturbance of 150 r/min was significant factors to decrease phosphine over the long term. Free phosphine had been detected but was of minor importance (in the order of 60.9+/-10.1 ng/m(3)). Overall, the fermentation conditions which had been most favorable for microbial life (moderate temperature (20 and 30 degrees C) and pH 8) were also most favorable for a positive phosphine balance. This is an indication, but no biochemical proof that a natural (biogenic, microbial, biochemical) NET PRODUCTION of phosphine or DE NOVO PRODUCTION of phosphine has occurred. MBP concentrations in lake sediments were discussed as to be strongly dependent on a balance of natural generation and depletion processes, dependent of the simulated parameters.

Temporal and spatial distributions of phosphine in Taihu Lake, China.

Phosphine is a natural gaseous carrier of phosphorus in its geochemical cycles, and it might be of importance to the phosphorus balance of eutrophic lakes. Phosphine concentration levels in Taihu Lake, a typical shallow eutrophic lake in China, were intensely investigated in this work. Results show that in the period of 2002 the variation of phosphine concentration in the atmosphere near Taihu Lake is significant, with a maximum value 2.85 pg/l. Concurrent sampling of phosphine in surface and bottom water of the lake had no distinct change. The mean concentration of phosphine in the water ranged from 1.92 to 3.01 pg/l. Approximately 84-90% of the phosphine was removed from lake water during passage of the sample through a 0.45 microm pore size filter, i.e. the average phosphine concentrations of filtered lake water in all sampling locations were from 0.37 to 0.40 pg/l with the highest value 0.73 pg/l and the lowest 0.08 pg/l, whereas phosphine concentrations in unfiltered samples were 5-9 times higher. Phosphine levels in lake sediments were positively correlated with different contamination of the samples. The concentration levels of phosphine were also higher in severe polluted sites. The local average values of the phosphine concentrations were from 21550 to 563,100 pg/kg. Its highest value was 919,238 pg/kg at 6# site (Zhihu harbor), a severely polluted sampling site.

Phosphine in various matrixes.

Matrix-bound phosphine was determined in the Jiaozhou Bay coastal sediment, in prawn-pond bottom soil, in the eutrophic lake Wulongtan, in the sewage sludge and in paddy soil as well. Results showed that matrix-bound phosphine levels in freshwater and coastal sediment, as well as in sewage sludge, are significantly higher than that in paddy soil. The correlation between matrix bound phosphine concentrations and organic phosphorus contents in sediment samples is discussed.

Phosphates, phosphites, and phosphides in environmental samples.

The common assumption that phosphorus occurs exclusively as phosphate in the environment is deserving of increased scrutiny. If a sample contained reduced phosphorus compounds (P in an oxidation state of less than +5), standard methods of phosphorus determination would incorrectly classify the compounds mostly as organic P, although significant fractions were sometimes misclassified as orthophosphates and condensed P. The disappearance of gaseous hydrogen phosphide (PH3) from samples was a function of solution composition, in that certain acids and metals enhanced removal whereas other constituents increased PH3 stability. No previously used extraction method could detect a significant portion of reduced phosphorus in representative samples by measuring PH3 evolution, particularly for highly recalcitrant iron phosphides. Despite analytical limitations, clear evidence was gathered that reduced phosphorus compounds can be leached from cast iron to water and that reduced phosphorus is also present in the scale (rust) that forms on the metal.