To understand the effect of high pressure on nitrogen oxides (NOx) formation in water added methane flames, opposed nonpremixed Water-methane/air (H2O-CH4/air) flames are numerically studied with high initial pressure. With GRI 3.0 detailed kinetic mechanism, NOx emissions are predicted for various strain rates. Due to high pressure, the chemical species are distributed in a narrow region, which means the thickness of the flame is thin. This can be clearly seen with high strain rate. Elevated pressure increases maximum temperature of flames which results in increased NOx emission. Even with elevated initial pressure, NOx emissions for H2O added methane flames are significantly decreased compare to pure methane flame. In addition, increased strain rate is also significant factor for decreasing NOx emission. With detailed rate of production analysis, in case of high pressure, it is confirmed that NO2 pathway is the most dominant reaction pathway than any other pathways.

The role played by reservoirs in the biogeochemical cycles of elements is a subject of ongoing debate. Recent research has revealed that reservoirs emit significant levels of greenhouse gases. To assess the importance of reservoirs in monsoon climate areas as a source of methane gas into the atmosphere, we investigated variations in organic carbon (OC) input into the reservoir, oxic state changes, and finally the amount of methane emitted (focusing on the ebullition pathway) in Lake Soyang, which is the largest reservoir in South Korea. Total organic carbon (TOC) concentrations were higher during summer after two years of heavy rainfall. The sedimentation rates of particulate organic carbon (POC) and particulate organic nitrogen (PON) were higher in the epilimnion and hypolimnion than the metalimnioin, indicating that autochthonous and allochthonous carbon made separate contributions to the TOC. During stratification, oxygen depletion occurred in the hypolimnion due to the decomposition of organic matter. Under these conditions, H2S and CH4 can be released from sediment. The methane emissions from the reservoir were much higher than from other natural lakes. However, the temporal and spatial variations of methane ebullition were huge, and were clearly dependent on many factors. Therefore, more research via a well-organized field campaign is needed to investigate methane emissions.

Seasonal emission characteristics of odors and methane were investigated throughout the period of 17 months in which the emission status of odors and methane from soil cover layers in a sanitary landfill was measured. Complex odor emitted from soil cover layers fluctuated largely at the range of 7~20,800 OU (Odor Unit) in odor dilution ratio, and the median and average values were 2,080 and 4,203 OU, respectively. The intensity of complex odor showed higher values in the spring (5,663 ± 4,033 OU) and winter (6,056 ± 8,372 OU) than in the summer (1,698 ± 3,676 OU) and fall (1,761 ± 451 OU). Based on average concentrations, the compounds with high contribution values for the sum of the odor quotient (SOQ) were hydrogen sulfide (46.1%), methyl mercaptan (26.4%), and dimethyl sulfide (16.8%). This result shows that sulfur compounds were the main odor-causing compounds in the target landfill. The flux of complex odor was 0.17~70.36 OU·m−2·min−1 (Median 0.47, Average 5.40), and the flux of hydrogen sulfide was 0~114.70 μg·m−2·min−1 (Median 0.13, Average 5.91). The methane flux was 0.59~312.70 mg-CH4·m−2·min−1 (Median 25.61, Average 47.99). The methane concentrations emitted at the soil cover layers showed the highest values of 1.0~62.5% (Median 33.0, Average 21.1) in the spring, and the lowest values of 0.1~11.7% (Median 2.3, Average 3.7) in the winter. The methane concentrations in the summer and fall were similar with the average of 17.9% (range of 0.2-44.2%) and 12.5% (range of 2.2-42.5%), respectively. The emission data of odors and methane from soil cover layers can be utilized to establish management policy and apply mitigation technologies for the control of odor and greenhouse gases emitted in landfills.

본 시험은 항염에 효과가 있다고 알려진 식물 추출물의 첨가가 반추위 발효와 메탄 생성에 미치는 영 향을 알아보기 위해 in vitro 실험을 수행하였다. 항염과 항산화 효과가 있는 산뽕나무, 뽕나무, 예덕나 무, 오동나무, 방아풀과 은행나무 6종을 선발하였다. 반추위액과 McDougall buffer 혼합액 15mL과 티 모시 0.3g, 각각의 추출물을 기질의 5%로 넣고 39℃에서 3, 9, 12, 24, 48 그리고 72시간 배양하였다. 항염 효과가 있는 식물 추출물의 첨가는 반추위 발효 성상(pH, 건물소화율, Glucose 농도, 암모니아 농도, 단백질 농도, 미생물 성장량, 휘발성지방산)에는 영향을 미치지 않았다. 총 가스 발생량은 각기 다른 양상을 보였으며, 이산화탄소 발생량은 48시간대에서 예덕나무와 방아풀에서 대조구에 비해 유의 적(p<0.05)으로 높았다. 또한 메탄 발생량은 배양 초기에는 대조구보다 첨가구에서 유의적(p<0.05)으로 감소하였으나, 발효가 진행될수록 대조구에 비해 첨가구에서 더 많은 메탄이 발생하였다. Polyphenol과 flavonoid는 은행나무 추출물구에서 가장 높았다. 본 시험의 결과에서 항염에 효과가 있는 식물 추출물 을 in vitro 반추위 배양액에 첨가하였을 때, 반추위 발효에는 영향을 미치지 않았고, 메탄은 초기 발효 에 저감 효과가 있는 것으로 사료된다.

본 연구는 약용실물 수피 추출물을 이용하여 in vitro 반추위 발효성상 및 반추위 메탄 발생에 미치 는 영향을 알아보기 위해 수행되었다. 공시재료는 무궁화, 음나무, 팽나무, 두충 및 후박나무 추출물을 사용하였다. McDougall’s buffer와 반추위액을 2:1 비율로 혼합한 발효액을 티모시 0.3g과 식물 추출 물이 담긴 50mL serum bottle에 혐기상태로 20mL 분주한 뒤, 39℃에서 3, 6, 9, 12, 24, 48 및 72시 간 동안 발효하였다. 약용식물 수피 추출물을 첨가하였을 때 반추위 발효 성상(pH, 건물소화율, 암모니 아태 질소, 미생물 성장량)에는 영향을 미치지 않았다. 배양 6시간대에 두충 추출물 첨가구에서 acetate의 농도가 대조구에 비해 유의적(p<0.05)으로 낮고, 메탄의 기질인 이산화탄소의 발생량이 대조 구에 비해 유의적(p<0.05)으로 낮아 메탄 저감 효과를 기대하였으나 메탄 저감효과는 없었다. 메탄생성 박테리아인 Methanogen archaea의 경우 무궁화 추출물 첨가구를 제외한 전 추출물 첨가구에서 대조구 에 비해 유의적(p<0.05)으로 높았으나 메탄발생량에는 유의적(p<0.05)인 차이가 없었다. 추후 첨가 농 도를 달리하거나 flavonoid 함량을 측정하는 실험이 필요한 것으로 사료되며, 메탄생성박테리아를 감소 시키는 연구도 추가적으로 필요할 것으로 생각된다

This study was conducted to investigate the effects of antiprotozoal plant extracts on in vitro ruminal fermentation and methane emission. Ruminal contents were collected from two ruminally-fistulated steers (Average BW: 450±30 kg) consuming 60% Timothy hay and 40% concentrate with free access to water and mineral block. Plant extracts, Lonicera japonica, Torreya nucifera, Zanthoxylum schinifolium, Poncirus trifoliate and Citrus junos, which have been known to have antiprotozoal and antiparasitic effects were added (5% of substrate) to the in vitro ruminal fermentation bottles containing the mixture of rumen fluid and McDougall’s buffer. The McDougall buffer (1000 ml) and ruminal inoculums (500 ml) were combined and 20 ml added to the 50 ml fermentation vessels containing 300 mg of substrate (DM basis). The fermentation vessels were placed in an incubator at 39°C for 3, 6, 9, 12, 24, 48 and 72 h with shaking. Plant extracts addition was decreased (p<0.05) acetate:propionate compared with control except with T. nucifera addition. Total gas production was increased (p<0.05), whereas methane emission was decreased (p<0.05) by all plant extracts compared with control at 12 h incubation. Methane emission at 24 h incubation was decreased for Lonicera japonica, Torreya nucifera, and Zanthoxylum schinifolium compared with control as well. In addition, methanogenic archaea was decreased (p<0.05) by all plant extracts at the 12 h incubation. These results indicate that the plant extracts may decrease methane emission by inhibiting methanogenesis without the decrease of total gas production in 12 h in vitro ruminal fermentation. Therefore, plant extracts which have the antiprotozoal effect may be promising feed additives for ruminants as a methane inhibitor

본 연구는 탄닌 함유 식물 추출물을 이용하여 in vitro 반추위 발효성상, 미생물 성장 및 메탄생성에 미치는 영향을 알아보고자 수행하였다. 반추위액은 농후사료와 조사료(timothy)를 40:60의 비율로 급 여한 반추위 cannula가 시술된 한우 암소에서 채취하였다. 본 실험에 사용한 식물 추출물은 상수리나 무(Quercus acutissima), 밤나무(Castanea crenata), 참가시나무(Quercus salicina), 졸참나무 (Quercus serrata) 그리고 떡갈나무(Quercus dentata)를 사용하였으며, 식물 추출물은 한국식물추출물 은행에서 분양받아 사용하였다. 반추위액과 McDougall buffer를 1:2의 비율로 혼합한 배양액을 0.3g timothy와 식물 추출물(기질의 5%)이 담긴 50mL serum bottle에 혐기상태로 15mL를 분주하였다. Serum bottle은 39℃, 120rpm으로 3, 6, 9, 12, 24, 48 및 72시간 동안 배양하였다. 본 실험 결과 배 양 시간이 지날수록 pH는 점점 감소하였으며, 정상범위에 포함되었다. 건물소화율은 대조구에 비해 첨 가구에서 유의적(p<0.05)으로 낮았다. 암모니아, 총 가스 생산량 및 이산화탄소 발생량은 대조구에 비 해 첨가구에서 유의적(p<0.05)으로 차이가 없었으나, 24시간 메탄 발생량은 대조구에 비해 전 첨가구에 서 유의적(p<0.05)으로 낮았다. 미생물 성장량은 첨가구에 따라 각각 다른 양상을 나타내었고, acetic acid 및 propionic acid는 대조구에 비해 첨가구에서 유의적(p<0.05)으로 낮았다. Real-Time PCR에서 섬유소 박테리아(R. albus, R. flavefaciens) 및 메탄 생성균(Ciliate associated methanogen)은 대조 군에 비해 유의적(p<0.05)으로 감소하였다. 결과적으로 본 실험에 사용한 탄닌 함유 식물 추출물 5종 모두 반추위 발효에 영향을 미치지 않으며, 메탄저감 효과를 나타내었다. 특히 상수리나무에서 반추위 발효성상에 악영향을 미치지 않으며 메탄 발생을 저감하는 식물 추출물로 적합하다고 생각된다.

An in vitro study was conducted to determine the effects of defaunation (removal of protozoa) and forage sources (rice straw, ryegrass and tall fescue) on ruminal fermentation characteristics, methane (CH4) production and degradation by rumen microbes. Sodium lauryl sulfate, as a defaunation reagent, was added into the mixed culture solution to remove ruminal protozoa at a concentration of 0.375 mg/ml. Pure cellulose (0.64 g, Sigma, C8002) and three forage sources were incubated in the bottle of culture solution of mixed rumen microbes (faunation) or defaunation for up to 24 h. The concentration of ammonia-N was high under condition of defaunation compared to that from faunation in all incubations (p<0.001). Total VFA concentration was increased at 3, 6 and 12 h (p<0.05~p<0.01) but was decreased at 24 h incubation (p<0.001) under condition of defaunation. Defaunation decreased acetate (p<0.001) and butyrate (p<0.001) proportions at 6, 12 and 24 h incubation times, but increased propionate (p<0.001) proportion at all incubation times for forages. Effective degradability of dry matter was decreased by defaunation (p<0.001). Defaunation not only decreased total gas (p<0.001) and CO2 (p<0.01~0.001) production at 12 and 24 h incubations, but reduced CH4 production (p<0.001) at all incubation times for all forages. The CH4 production, regardless of defaunation, in order of forage sources were rice straw > tall fescue > ryegrass > cellulose (p<0.001) up to 24 h incubation.

고형페기물 매립지에서 온실가스 배출량 산정은 기후변화에 대응 측면에서 매우 중요한 사항이다. 국내에서 메탄가스 배출량 산정은 주로 IPCC(Intergovernmental Panel on Climate Change)가이드라인에 근거하여 매립지 표면에서 직접적으로 flux chamber를 이용하여 배출량을 측정하거나, 또는 FOD(First Order Decay)방법에 의존하여 왔다. 그러나 FOD방법은 매립특성을 반영한 매립가스발생속도상수(k)를 정확히 산정하는데 어려움이 존재하고, 또한 표면 발산량을 측정하는 방법은 매립지 표면에서 배출량이 다양하고 측정이 한정된 기간에만 국한된다는 문제점을 내재하고 있다. 대안으로 본 연구에서는 plume measurement의 한 방법으로 대기확산모델을 활용한 역모델링기법을 적용하는 것을 검토하였다. 역모델링에 의해서 매립지 메탄가스 배출량을 직접 계산하기 위한 방법론을 정리하고, 실제 대전매립지에서 측정한 메탄농도를 이용하여 역모델링기법을 적용한 매립지 메탄 배출량 산정하는 방법에 대하여 제시하였다. 역모델링 과정을 검증하기 위해서 임의의 배출량으로 모델링을 수행하여 모델 예측농도와 확산변수 를 계산하였으며, 역으로 예측농도와 확산변수 를 이용하여 배출량을 재산정 하였다. 재산정한 배출량이 임의의 배출량과 동일함을 확인함으로써 본 연구에서 제시하고 있는 역모델링 절차가 적절함을 검증하였다. 또한, 본 연구에서는 역모델링 기법을 적용하여 실제 대전매립지를 대상으로 메탄 배출량 산정하였다. 대전매립지를 대상으로 메탄배출량을 산정한 결과 29.65~36.68 g/㎡-day로 산정되었으며, 주요 메탄 배출지점은 매립지 내의 유사한 지점에서 일관되게 나타났다. 본 연구방법은 기존의 방법과 비교하면, 메탄농도의 측정방법이 간단하고 비용이 적게 소요되므로 지속적인 모니터링이 가능한 장점이 있으며, 불균일한 매립지 표면의 배출량을 비교적 간편하게 산출이 가능한 것으로 파악되었다. 한편, 본 연구는 제한된 실험에 의한 결과이므로 향후 실제 매립지 배출량을 직접 측정하거나, 또는 추적자 실험을 통해서 그 방법론을 추가로 검증할 필요가 있는 것으로 판단된다.

This study was conducted to investigate for the natural methane emission inhibitor as a feed additive no adversely effect on rumen fermentation. Five different Control (Wheat barn (0.05 g), MRA(Methane Reduction Additive)-1 (Allium fistulosum L. (0.05 g)), MRA-2 (Sodium Lauryl Sulfate (0.025 g) +Wheat barn (0.025 g) mixed), MRA-3 (Sodium Dodecyl Sulfate (0.025 g) + Wheat barn (0.025 g) mixed), and MRA-4 (Allium fistulosum L. (0.02 g) + Tannic acid (0.02 g) + Wheat barn (0.01 g) mixed) contents were used to perform 3, 6, 9, 12, 24 and 48 h incubation for in vitro fermentation. Ruminal pH values were ranged within normal ruminal microbial fermentation. Dry matter digestibility was not significantly different across the treatments during the whole fermentation time. Also, the result of microbial growth had no adversely effect on during the whole fermentation time. At 24 h, methane emission was significantly lower (P<0.05) than all treatments except to MRA-1. Especially, MRA-4 carbon dioxide emission was significantly lower (P<0.05) than control at 9, 24 and 48 h incubation. In addition MRA-4 propionate concentration was significantly higher (P<0.05) than control at 24 h incubation. The result of RT-PCR Ciliate-associated methanogens were significantly lower (P<0.05) at MRA-1, MRA-3 and MRA-4 than control at 24 h incubation. Based on the present results, MRA-4 could be suggestible methane emission inhibitor as a natural feed additive.

Livestock manure treatments have become a more serious problem because massive environmental pollutions such as green and red tides caused by non-point pollution sources from livestock manures have emerged as a serious social issue. In addition, more food wastes are being produced due to population growth and increased income level. Since the London Convention has banned the ocean dumping of wastes, some other waste treatment methods for land disposal had to be developed and applied. At the same time, researches have been conducted to develop alternative energy sources from various types of wastes. As a result, anaerobic digestion as a waste treatment method has become an attractive solution. In this study has three objectives: first, to identify the physical properties of the mixture of livestock wastewater and food waste when combining food waste treatment with the conventional livestock manure treatment based on anaerobic mesophilic digestion; second, to find the ideal ratio of waste mixture that could maximize the collection efficiency of methane (CH4) from the anaerobic digestion process; and third, to promote CH4 production by comparing the biodegradability. As a result of comparing the reactors R1, R2, and R3, each containing a mixture of food waste and livestock manure at the ratio of 5:5, 7:3, and 3:7, respectively, R2 showed the optimum treatment efficiencies for the removal of Total Solids (TS) and Volatile Solids (VS), CH4 production, and biodegradability.

This study was conducted to evaluate Raphanus sativus extracts to methane reduction in rumen. Five different levels of R. sativus extracts were used to investigate the most effective dosing level for the decrease of methane production in the rumen. The rumen fluid was collected from a cannulated one Hanwoo cow (BW=450±30 kg) consuming 600 g/kg timothy and 400 g/kg concentrate. On fermentation day, rumen fluid was collected at 2 hr postfeeding R. sativus extracts was dosed to achieve final concentration of 0, 1, 3, 5, 7, and 9% respectively, to fermentation bottles containing the mixture of rumen fluid and McDougall’s buffer and 300 mg of timothy was added as a substrate. The fermentation was conducted for 3, 6, 9, 12, 24, 48 and 72 hr incubation time at 39℃ with shaking. In vitro ruminal pH values were measured normal range for ruminal fermentation. Dry matter disappearance was significantly higher (p<0.05) at 3 hr incubation time 1, 3 and 5% doses than that of control. The highest methane reduction was observed in 12 hr incubation time 5, 7 and 9%. The carbon dioxide emission was also significantly (p<0.05) lower than that of control at 12 hr incubation time 5, 7 and 9%. The total volatile fatty acid was no significant difference between control and all doses level at 12 and 24 hr incubation time. At 24 hr incubation time, the result of real-time PCR were indicated that M. archea was significantly lower (p<0.05) at all doses level comparing to that of control. In conclusion, R. sativus extracts were significantly decreased methane emission. R. sativus extracts were significantly lower (p<0.05) than that of control at 12 hr incubation time 5, 7 and 9% and no adversely effect in rumen pH, dry matter disappearance and total VFA.

우리나라 폐기물관리법(구폐기물관리법)에서는1997년 재활용 규정을 제정한 이후, 사업장일반폐기물 중 석탄재, 점토점결주물사, 광재 및 무기성오니 등은 성토재 등으로 재활용할 수 있도록 해왔다. 그러나 해당 폐기물에는 아연, 납, 불소 등의 성분이 현행 토양오염 우려기준을 초과하는 경우가 있어, 과거 적법한 절차를 거쳐 폐기물을 재활용하였더라도 토양환경보전법에 따라 부지정화를 시행하는 사례가 종종 보고된다. 과거 폐기물을 성토재 등으로 재활용한 지역의 부지정화를 시행하는 경우, 토양과 폐기물은 최대한 분리/선별한 후에 각각 토양환경보전법과 폐기물관리법에 따라 처리하는 것이 원칙이다. 또한, 토양정화 비용과 폐기물처리 비용이 차이를 고려할 때, 경제적인 측면에서도 토양과 폐기물을 분리하는 것이 매우 중요하다. 하지만, 앞서 언급한 석탄재 등의 폐기물은 육안상 토양과 구별이 어렵고, 물리적 성상(입도 및 밀도) 또한 토양과 유사하기 때문에 일반적인 방법으로는 선별이 불가능한 문제가 있다. 본 논문에서는 TPH, 아연, 비소 등이 1지역 토양오염우려기준을 초과하는 폐기물 재활용지역을 대상으로 XRF분석을 실시하였고, 조사결과를 토대로 오염토양과 폐기물에 대한 분류기준 수립하고 ‘토양환경보전법’과 ‘폐기물관리법’의 적용여부를 판단하는 자료로 활용하고자 하였다. XRF를 이용하여 측정한 주요 성분을 ternary diagram (SiO2, CaO/MgO, Al2O3/Fe2O3/기타)을 이용하여 비교하였으며, 오염토사와 폐기물은 성분비에 따라 구별이 가능함을 확인하였다. 토양오염도 조사결과 폐기물시료의 TPH, 아연, 비소의 농도는 토양에 비해 3~4배 정도 높게 측정되어, 폐기물을 분리/선별하는 것만으로도 토양오염도를 상당 부분 낮출 수 있을 것으로 기대된다.

우리나라의 메탄가스 배출량은 2014년 기준 26.6백만톤 CO2eq 수준으로, 이중 약 27% (7.3 백만톤 CO2eq)는 폐기물매립지에서 유출되고 있다. 매립지에서의 메탄유출을 저감하는 가장 이상적인 방법은 매립가스를 포집하여 에너지화하는 “매립가스 자원화” 방식이다. 그러나, 이를 위해서는 가스포집시설, 가스정제시설 및 발전설비 등의 설비투자가 필요하며, 매립가스 발생량이 2~3 N㎥/min (메탄가스 농도 35%~50%)이상의 대규모 매립지에서만 경제성 확보가 가능하다고 알려져 있다. 이런 이유로 230개소의 매립지 중 17개 시설에서만 매립가스 자원화 시설을 운영하고 있으며, 대부분의 중소규모 매립지에서는 메탄유출에 대한 별다른 대책이 없는 실정이다. 본 연구에서는 중소규모의 매립지 5개소를 선정하여 “공기주입을 통한 호기성 매립지 전환” 및 “매립지복토층을 이용한 생물학적 메탄산화 기술”의 메탄저감 성능과 경제성을 검토하였고 “매립가스 자원화”와 비교하였다. 매립가스 자원화를 검토하기 위한 매립가스 발생량은 LandGem 모델을 이용하여 산정하였으며, 폐기물의 성상(메탄잠재발생량 및 메탄발생속도추정)및 매립량은 환경부 통계자료를 이용하였다. 공기주입에 따른 호기성전환 비율은 주입압에 따른 유효반경을 산정하여 추정하였으며, 복토층에서의 메탄산화 효율은 문헌조사를 통해 결정하였다. 기술검토 결과 공기주입과 복토층 메탄산화기술을 조합하는 경우 70~85% 수준까지 메탄유출을 저감할 수 있는 것으로 추정되었으며, 중소규모 매립지의 경우 매립가스 자원화와 비교하여 상대적으로 우수한 경제성을 나타냈다.

Livestock manure treatments have become a more serious problem because massive environmental pollutions such as green and red tides caused by non-point pollution sources from livestock manures have emerged as a serious social issue. In addition, more food wastes are being produced due to population growth and increased income level. Since the London Convention has banned the ocean dumping of wastes, some other waste treatment methods for land disposal had to be developed and applied. At the same time, researches have been conducted to develop alternative energy sources from various types of wastes. As a result, anaerobic digestion as a waste treatment method has become an attractive solution. In this study has three objectives: first, to identify the physical properties of the mixture of livestock wastewater and food waste when combining food waste treatment with the conventional livestock manure treatment based on anaerobic mesophilic digestion; second, to find the ideal ratio of waste mixture that could maximize the collection efficiency of methane (CH4) from the anaerobic digestion process; and third, to promote CH4 production by comparing the biodegradability. As a result of comparing the reactors R1, R2, and R3, each containing a mixture of food waste and livestock manure at the ratio of 5:5, 7:3, and 3:7, respectively, R2 showed the optimum treatment efficiencies for the removal of Total Solids (TS) and Volatile Solids (VS), CH4 production, and biodegradability.

This study was conducted to serve as the basis for establishing a standard cultivation, which enhances the alternative utilization of pig manure, a major cause of environmental pollution, by finding a means for reducing greenhouse gas emissions for eco-friendly cultivation. In a laboratory, CH4 and CO2 emission patterns were investigated corresponding to incremental pig manure treatments in paddy soil. The emissions peaked 12 to 27 days after manure application in the 100~400% applications. It was found that increasing applications of pig manure resulted an increase in CH4 and CO2 emissions. Additionally, application of more than 150% emitted a larger amount of these gasses than applying chemical fertilizer. However, the test application of 100% pig manure emitted a smaller amount of CH4 and hence Global Warming Potential (GWP) than those emitted by chemical fertilizer. If appropriate amount of fertilization is applied in compliance with the standard application rate, the pig manure may be effective in reducing greenhouse gas emissions and the soil environment made more favorable than with the use of chemical fertilizer.