On East Asian Sand and Duststorms and Associated Significant Dustfall Observed from January to May 2001

Monitoring of dust pollution at the western shore of Tae-ahn Peninsula (TAP) and in the Chongju area of central Korea was carried out from January to May 2001. It was found that in Koreathere were 9 cases of sand and duststorms (DS) and 16 associatedsignificant dustfall (SD) days. Observed maximum concentrations of DS and SD coming from NW China and Mongolia were in the rangeof 300–920 for TSP, 200–690 for PM₁₀ and 100–170 g m^-3 for PM_2.5.Satellite measurements clearly showed the formation and subsequent movement of DS to the Korean Peninsula and onward to the Korea East Sea, Japan and the Gulf of Alaska. According to satellite image analysis of dust clouds there were abundant coarse particles, measuring in size of 11.0 m. Medium-sizedparticles measuring in the range of 3.5–7.0 were also prevalent,while fine particles of less than 2.0 m were less distinctive in reflectivity. Measured values of PM_2.5 were alsorelatively low with SD events.The measured average pH values of dusty precipitation associatedwith DS were 7.24. Alkaline precipitation can play a `temporary'role in the neutralization of acidified soil until the subsequentevent of acidic rain. The new selection criteria of SD days from PM_2.5 at 85 g m^-3, PM₁₀ 190 g m^-3 and TSP 250 g m^-3 are recommended on dust pollution occurring from the invasion of a DS elsewhere.     

A carbon-13 method for evaluating degradation of starch-based polymers

A new method for evaluating biodegradability of starch-based and certain other polymer blends uses the pre- and postexposure stable carbon isotope composition of material coupled with weight loss data to determine which components have degraded. The naturally occurring stable isotope of carbon.¹³C, is enriched in corn starch (¹³C, approx. –11) compared to petroleum-derived synthetic polymers (¹³C, approx. –32). Results on starch-synthetic polymer blends indicate that the ¹³C signatures of these blends are near-linear mixtures of their component ¹³C. Values of a ¹³C for starch-synthetic polymer blends exposed to biologically active laboratory soil and artificial seawater conditions are depleted in¹³C compared to unexposed samples, suggesting loss of the starch component. Combined with weight loss data for the exposed samples, the ¹³C values are statistically consistent with models requiring loss of the soluble component glycerin, followed by loss of starch, then petrochemical polymer, or simultaneous loss of starch and petrochemical polymer. Replicate ¹³C analyses of starch-synthetic polymer blends increase the statistical power of this relatively inexpensive, accessible technique to discriminate between degrading components.     

Ring-Opening Polymerization of Cyclic Esters onto Liquefied Biomass

Ring-opening polymerization of cyclic esters (-caprolactone, -valerolactone, and l-lactide) onto liquefied biomass (LB) was conducted to obtain the polyester-type polyol and to regulate the characteristics of LB. IR and ¹H-NMR spectra of the obtained polyol showed that the polymerization was successfully conducted in the presence of acid catalyst, which is used in liquefaction. The molecular weight (M_w), hydroxyl value, and viscosity were controllable by changing the reaction conditions. Polyester-type polyurethane foams with a wide range of properties were prepared from the obtained polyol with the appropriate combinations of foaming agents.     

Novel Biobased Polyurethanes Synthesized from Soybean Phosphate Ester Polyols: Thermomechanical Properties Evaluations

Biobased polyurethanes from soybean oil–derived polyols and polymeric diphenylmethane diisocyanate (pMDI) are prepared and their thermomechanical properties are studied and evaluated. The cross-linked biobased polyurethanes being prepared from soy phosphate ester polyols with hydroxyl contents ranging from 122 to 145 mg KOH/g and pMDI within 5 min of reaction time at 150°C in absence of any catalyst show cross-linking densities ranging from 1.8 × 10³ to 3.0 × 10³ M/m³, whereas glass transition temperatures vary from approximately 69 to 82°C. The loss factor (tan ) curves show single peaks for all these biobased polyurethanes, thus indicating a single-phase system. The storage moduli (G) at 30°C range from 4 × 10⁸ to 1.3 × 10⁹ Pa. Upon postcure at 150°C, the thermomechanical properties can be optimized. Cross-link densities are improved significantly for hydroxyl content of 139 and 145 mg KOH/g at curing time of 24 h. Similarly, glass transition temperature (T_g) and storage moduli around and after T_g are increased. Meanwhile, tan intensities decrease as result of restricted chain mobility. Longer exposure time (24 h) induces thermal degradation, as evidenced by thermogravimetric analysis (TGA). The dynamic mechanical (DMA) analysis shows that postcure at 100°C for times exceeding 24 h also leads to improved properties. However, cross-linking densities are lower compared to postcure carried out at 150°C.     

Study on the conversion of waste plastics/petroleum resid mixtures to transportation fuels

Catalytic coprocessing of model and waste plastics with light Arabian crude oil residue was investigated using NiMo/Al₂O₃, ZSM-5, FCC, and hydrocracking catalysts. Reaction systems that were studied included low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), and polypropylene (PP). A series of single (plastic/catalyst) and binary (plastic/resid/catalyst) reactions were carried out in a 25-cm³ micro autoclave reactor under different conditions of weight and type of catalyst, duration, pressure, and temperature. The optimum conditions selected for our work were: 1% catalyst by weight of total feedstock weight, 60min reaction time, 8.3Mpa of H₂, and 430°C. The product distribution for the binary system using plastic and petroleum residue provided some encouraging results. High yields of liquid fuels in the boiling range of 100°–480°C and gases were obtained along with a small amount of heavy oils and insoluble material such as gums and coke. In general, this study helps to demonstrate the technical feasibility of upgrading both waste plastics and petroleum resid, as well as an alternative approach to feedstock recycling.     

Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Synthesis of a block copolymer of poly(3-hydroxybutyrate) and poly(ethylene glycol) and its application to biodegradable polymer blends

A block copolymer {P[(R,S)-HB-b-EG]} of atactic poly[(R,S)-3-hydroxybutyrate] {P[(R,S)-HB]} and poly(ethylene glycol) (PEG) was prepared by the ring-opening polymerization of -butyrolactone in the presence of a macroinitiator (PEG/ZnEt₂/H₂O) which had been produced by the reaction of ,-dihydroxy PEG ( _n=3000) with ZnEt₂/H₂O (1/0.6) catalyst. The block copolymer ( _n=10,500, _w/ _n=1.2) was an A-B-A triblock copolymer comprising atactic P[(R,S)-HB] (A) and PEG (B) segments. The miscibility, physical properties, and biodegradability of binary blends of microbial poly[(R)-3-hydroxybutyrate] {P[(R)-HB]} with the block copolymer P[(R,S)-HB-b-EG] has been studied. The glass-transition temperature (T _g) data showed that the P[(R)-HB]/P[(R,S)-HB-b-EG] blend was miscible in the amorphous state. The P[(R)-HB] film became flexible and tough by means of blending with P[(R,S)-HB-b-EG] block copolymer. The enzymatic degradation of blend films was carried out at 37°C and pH 7.4 in a 0.1M phosphate solution of an extracellular PHB depolymerase fromAlcaligenes faecalis. The enzymatic degradation took place solely on the surface of the blend films.     

Hysteresis in Reversal of Central European Mountain Lakes from Atmospheric Acidification

Extremely high emissions of S and N compounds in Central Europe (both 280 mmol m^-2 yr^-1) declined by 70and 35%, respectively, during the last decade. Decreaseddeposition rates of SO₄ ^-2, NO₃ ^-, and NH₄ ⁺ in the region paralleled emission declines. The reduction in atmospheric inputs of S and N to mountain ecosystemshas resulted in a pronounced reversal of acidification in the Tatra Mountains and Bohemian Forest lakes. Between the 1987–1990and 1997–1999 periods, concentrations of SO₄ ^-2 and NO₃ ^- decreased (average ± standard deviation) by 22±7 and 12±7 mol L^-1, respectively, in theTatra Mountains, and by 19±7 and 15±10 mol L^-1, respectively, in the Bohemian Forest. Their decrease was compensated in part (1) by a decrease in Ca²⁺ + Mg²⁺ (17±7 mol L^-1) and H⁺ (4±6 mol L^-1), and an increase in HCO₃ ^-(10±10 mol L^-1) in the Tatra Mountains lakes, and (2) by a decrease in Al (7±4 mol L^-1), Ca²⁺ + Mg²⁺ (9±6 mol L^-1), and H⁺ (6±5 mol L^-1), in Bohemian Forest lakes. Despite the rapid decline in lake water concentrations of SO₄ ^-2 and NO₃ ^- in response to reduced S and N emissions, their present concentrations in some lakes are higher than predictionsbased on observed concentrations at comparable emission rates during development of acidification. This hysteresis in chemical reversal from acidification has delayed biological recovery of the lakes. The only unequivocal sign of biological recovery hasbeen observed in erné Lake (Bohemian Forest) where a cladoceran species Ceriodaphnia quadrangular has recentlyreached its pre-acidification abundance.     

Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Effect of Crystalline and Amorphous Structures on Biodegradability of Poly(Tetramethylene Succinate)

The effect of orientation in the amorphous and crystalline regions on the biodegradability of PTMS [poly(tetramethylene succinate)] was studied using the amorphous orientation function, birefringence, and crystallinity. The crystalline and amorphous intrinsic lateral sonic moduli, E _t,c ⁰ and E _t,am ⁰ , were 2.61 × 10³ and 0.41 × 10³ MPa, respectively. Using the data on birefringence, crystalline and amorphous orientation function (f and f _am), crystallinity, and sonic modulus of the oriented PTMS fibers, the intrinsic birefringence of the crystalline ( _c ⁰ ) and amorphous ( _am ⁰ ) regions were evaluated to be 0.0561 and 0.0634, respectively. The biodegradabilities of oriented PTMS films were reduced as the elongation increased, i.e., the amorphous orientation increased. At low elongation (100 and 150%), however, biodegradabilities remained unchanged when the degradation test was performed in activated sludge, which was attributed to the amorphous orientation occurring even at 100% elongation, though the amorphous orientation direction was perpendicular to the fiber axis.     

Physical Modelling of Urban Roughness using Arrays of Regular Roughness Elements

The aerodynamic behaviour of large urbanagglomerations must be represented in increasingly greaterdetail, as large-scale numerical weather prediction and airpollution dispersion models are refined. The present studyprovides detailed measurements of the flow field in regulararrays of obstacles to obtain representative data on meanflow and turbulence statistics in urban-type areas. Obstacle arrays consisting of simple cubes and flat plateroughness commonly used in boundary layer simulations wereplaced in a simulated atmospheric boundary layer flow in ahydraulic flume. The scale factor was about 1:200 based onthe obstacle height (50 mm). The results show noappreciable `constant stress' region in the internalboundary layer above the buildings, since in any finite-length test array the boundary layer is always developing.However, if the RMS turbulence components are scaled by thelocal values of the shear stress, then there seems to be auniversal scaling, with _u/u_* = 2.1,_v/u_* = 1.65 and _w/u_* = 1.2. This greatly simplifies the parameterization of the first orderturbulence statistics in obstacle arrays. It was alsoobserved during the experiments that, compared to results inthe cube arrays, the turbulence kinetic energy and theReynolds stresses were almost doubled in the flat plateroughness arrays.     

Thermal cracking of oils from waste plastics

Thermal cracking of decomposed waste plastic oil produces a good yield of olefins. The solvent extraction of such waste plastic oil seems to be efficient for increasing gas yields and recycling monomers. To assess the potential of monomer recovery from municipal waste plastics, the oils were cracked using a laboratory-scale quartz-tube reactor. The waste plastic oils were provided by two commercial plants of the Sapporo Plastic Recycle Co. and the Dohoh Recycle Center Co. in Japan. A model waste plastic oil made in a laboratory was also examined. Yields of ethene, propene, and other products were measured at different temperatures. Two-step pyrolysis reduces coking compared with the direct thermal degradation of plastics. The raffinates from waste plastic oils extracted by sulfolane were also cracked. The primary products were almost the same as those from nontreated oils. The maximum total gas yield was 78wt%–85wt% at 750°C, an increase of about 20wt% compared with that of nonextracted oil. Solvent extraction removes stable aromatic hydrocarbons such as styrene, which is more coked than cracked.     

Formation of Reactive Gaseous Mercury in the Arctic: Evidence of Oxidation of Hg° to Gas-Phase Hg-II Compounds after Arctic Sunrise

We have measured total gaseous mercury concentrations(Hg°) at Point Barrow, Alaska since September 1998 in aneffort to determine the geographic extent and reaction mechanismof the so-called mercury depletion events (MDE) previouslyreported in the high Arctic at Alert, Canada. Hg° has beensampled now for nearly 2 years at Barrow. In September, 1999, webegan making the first automated measurements of reactive gaseousmercury (RGM) attempted in the Arctic, along with measurements ofHg accumulation in snowpack to determine the fate of the depleted Hg°. During the fall and early winter, Hg°and RGM exhibit only minor variation, Hg° remaining within10% of global background, near 1.6–1.8 ng m^-3. The MDEperiods are quite different, however; within days of Arcticsunrise in January, Hg° exhibits major variations from themean, rapidly dropping as low as 0.05 ng m^-3 and then cyclingback to typical levels, sometimes exceeding global background. These events continue throughout Arctic spring, then end abruptlyfollowing snowmelt, in early June. Prior to Arctic sunrise, RGMremains near detection (<2 pg m^-3), but after sunriseincreases dramatically (to levels as high as 900 pg/m³) insynchrony with the depletion of Hg°. Both phenomenaexhibit a strong diel cycle, in parallel with UV-B. We concludethat MDE's involve rapid in-air oxidation of Hg° to aspecies of RGM by photochemically-driven reactions, probablyinvolving the same reactive bromine and chlorine compoundsinvolved in ozone destruction. Sharp increases in Hg in thesurface snowpack after sunrise coincident with periods of peakRGM suggest surface accumulation of the RGM by dry deposition.     

Enzyme-Mediated Reactions of Oligosaccharides and Polysaccharides

Two types of enzymatic reactions are given here as examples of synthetic problems encountered in industry. In the first case, commercially available -D-galactosidase from Escherichia coli was used as a catalyst to transfer galactose from -lactose to oligosaccharides. A preference for galactosyl transfer to the 3- or 4-position of the sugar moiety of the oligosaccharide was observed for the products. As expected, only the -anomer was produced. A wide variety of sugars, including disaccharides, trisaccharides, cellotetraose, and maltodextrins, has been shown to act as acceptors, yielding oligosaccharides. In the second example, -galactomannan that had been previously treated to contain cationic groups (cationic guar gum) was subjected to treatment with a series of inexpensive commercial enzymes such as lipases, protease, and cellulases. Some enzyme preparations showed significant changes in the viscosities of 1% cationic guar solution. For example, lipases from Aspergillus niger and Aspergillus saitoi and protease XIII from Rhizopus niveus produced a substantial viscosity reduction (0–20% of original viscosity). These examples demonstrate the utility of low-cost enzymes in manipulating polymer structures.     

The release of nitrous oxide from the intertidal zones of two European estuaries in response to increased ammonium and nitrate loading

Nitrous oxide (N₂O) release and denitrification rates were investigated from the intertidal saltmarsh and mudflats of two European river estuaries, the Couesnon in Normandy, France and the Torridge in Devon, UK. Sediment cores and water were collected from each study site and incubated for 72 h in tidal simulation chambers. Gas samples were collected at 6 and 12 h intervals from the chambers during incubation. From these N₂O emission rates were calculated. The greatest rates for both N₂O production and denitrification were measured from saltmarsh cores. These were 1032 mol N₂O m^–2 day^–1 and 2518 mol N₂ m^–2 day^–1, respectively, from the Couesnon and 109 mol N₂O m^–2 day^–1 and 303 mol N₂ m^–2 day^–1 from the Torridge. A strong positive correlation was apparent with N₂O emission rates and ammonium concentration in the sediment, nitrate concentration in floodwater and sediment aerobicity.     

Biodegradability of Thermally Aged PHB,PHB-V,and PCL in Soil Compostage

The biodegradability of poly--hydroxybutyrate (PHB), poly--hydroxybutyrate-co-valerate (PHB-V) and poly--caprolactone (PCL) were examined following thermal aging in an oven for 192, 425 and 600 h. Different temperatures, 100, 120 and 140°C for PHB and PHB-V and 30, 40 and 50^oC for PCL were used to assess the influence of this parameter on biodegradation. The biodegradability tests were done in soil compostage at pH 11.0 and involved measuring the residual mass of polymer. Thermal analysis of the polymers was done using a differential scanning calorimeter (DSC). The melting temperature and crystallinity were also determined. Thermal ageing increased the biodegradability only for PHB at 120 and 140^oC, and there was no correlation between crystallinity and the biodegradation of the polymers.     

Comparison of the Chemical Composition of Mineral Particles Collected in Dunhuang,China and those Collected in the Free Troposphere over Japan: Possible Chemical Modification during Long-Range Transport

The Asian continent is recognized as one of the most important sources of mineral (or soil) particles. These particles have a large potential to effect global changes through the biogeochemical cycle of particulates and through radiative balance (IPCC Third Assessment Report, 2001). Therefore, comparison of particle compositions near the source region and those after long-range transport is important in understanding the long-range particle transport phenomenon. Individual aerosolparticles were collected in Dunhuang (40°09N; 94°41E), China. Particles were collected at the campus of the Meteorological Bureau of Dunhuang City (17 August 2001) and near the Mogao Grots, located approximately 30 km from Dunhuang (18 August 2001, 18 October 2001 and 13 January 2002) using a two-stage low-volume impactor. The morphology of individual aerosol particles and their elemental compositions were examined via a scanning electron microscope (Hitachi, S-3000N) equipped with an energy dispersive X-ray (EDX) analyzer (Horiba, EMAX-500). The particles collected at these locations were comprised primarily of minerals, with the exception of sulphateparticles in the submicron range that were contained in thesample collected on 18 October 2001 (likely, ammonium sulphate). The most abundant elements were found to be Si and Al. Approximately 46–77% of the collected particles were Si-richparticles (composed primarily of quartz and aluminosilicate),and 13–41% of the collected particles were Ca-rich particles,such as calcite (CaCO₃), dolomite (CaMg(CO₃)₂),and gypsum (CaSO₄2H₂O). The fractions of Fe-rich, Mg-rich, Ti-rich, K-rich, and Cl-rich were 3–10, 0–7, 0–3, 0–1, and 0–1%, respectively. Similar types of mineral particles were found in the free troposphere over Japan(Trochkine et al., 2002). A number of differences were found to exist between the particles collected in China and thosecollected in Japan, and these differences can be explained bychemical modification of the particles during transport fromChina to Japan.     

Electrosynthesis of κ-Carrageenan Complexes with Gelatin

Electrosynthesis at pH 9, 12, and 11 of -carrageenan–gelatin complexes from electrolytes containing the components at proportions varying from 1:5 to 5:1 provided complexes in the composition varying in a range from 1:10 to 1:1.8. Components were bound mainly electrostatically, although partial insolubility of complexes in 7 M aqueous urea pointed to a part of the complexes bound covalently. None of the performed tests except solubility could confirm formation of covalent complexes. The complexation of -carrageenan to gelatin significantly increased the thermal stability of carrageenan, whereas the thermal stability of gelatin increased rather insignificantly.     

Correlating the Spatial Distribution of Atmospheric Ammonia with δ15N Values at an Ammonia Release Site

A field ammonia (NH₃) release experiment and open top chambers containing moorland monoliths continuously fumigated with NH₃ or sprayed with NH₄Cl were used to assess the potential for using ¹⁵N values in determining the area of influence around a point NH₃ emission source. ¹⁵N values are being increasingly used as environmental tracers and we tested the hypothesis that the ¹⁵N signal from an NH₃ emission source is observable in nearby vegetation. Using modified monitoring devices, atmospheric NH₃ concentrations were found to decrease with distance from source, with ¹⁵N values also reflecting this trend, producing a signal shift with changing concentration. Open top chamber studies of ¹⁵N values of Calluna vulgaris (L.) Hull indicated a correlation with deposition treatments in current year shoots. Analysis of Calluna shoots from the NH₃ release showed a similar trend of ¹⁵N enrichment. Significant linear correlations between ¹⁵N and percent N in plant material were found, both in the controlled conditions of the open top chambers and at the NH₃ release site, illustrating the possible use of this technique in N deposition biomonitoring.     

Effects of Lime and Ash Treatments on DOC Fractions and Low Molecular Weight Organic Acids in Soil Solutions of Acidified Podzolic Soils

Dissolved organic carbon (DOC) fractions and different low molecular weight organic acids (LMWOAs) were determined in soil solutions from two lime or ash treated Norway spruce sites in the south of Sweden. At Hasslöv, 3.45 t ha^-1 or 8.75 t ha^-1 dolomite were applied 15 years before sampling. Horröd was treated with 4.28 t ha^-1 ash and 3.25 t ha^-1 dolomite and sampled four years later. Propionate (7–268 M) and malonate (2–34 M) were the LMWOAsfound in the highest concentrations at Hasslöv. Two other LMWOAs dominated at Horröd, namely citrate (18–64 M)and fumarate (5–31 M). The differences in concentration of most of the determined LMWOAs at Hasslöv were significantly increased due to treatment. The LMWOAs comprised between 1.1–6.3% of the DOC at Hasslöv and 4.5–17.6% at Horröd. At Hasslöv normally 3–10% of the total acidity (TA) was due to LMWOAs and the average specific buffer capacity was 74 ± 22 mmol mol^-1C.The total DOC concentration in the mor layer solution was 16 mM for the dolomite treated plots compared to 10 mM at the untreated plot. A major part of the increase in DOC at the treated plots apparently had a hydrophobic character and was of high molecular weight corresponding to 3–10 kDa. The concentration of DOC < 1 kDa in the control and treated plots was similar.